CN1861257A - Treatment method before application of hydrogenation catalyst - Google Patents
Treatment method before application of hydrogenation catalyst Download PDFInfo
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Abstract
A process for treating the hydrocatalyst before it is used features that the organic solvent and sulfur-contained substance are introduced to the oxidation-state hydrocatalyst for higher activity.
Description
Technical field
The present invention relates to the processing method before a kind of hydrogenation catalyst is used, particularly before catalyst is used for hydrogenation reaction, introduce the processing method of elementary sulfur on the device of other outside reactor.
Background technology
Hydrogenation catalysts such as hydrofinishing, hydrotreatment, hydrocracking are carrier with refractory oxides such as aluminium oxide, sial, molecular sieves generally, one or more are active metal component with molybdenum, tungsten, cobalt, nickel etc., can also contain adjuvant components such as phosphorus, silicon, fluorine, titanium, zirconium, boron in the catalyst sometimes.The metal component of the general catalyst that obtains in process of production exists with oxidation state, and in hydrogenation process, the activity of such catalysts metal component is in sulphided state, and (metal exists with oxide morphology: Co
9S
8, MoS
2, Ni
3S
2, WS
2Deng) time have higher reactivity worth, therefore, before catalyst uses, need to change its presulfurization into sulphided state.Yet the effect and the catalytic performance of presulfurization are in close relations, and the method for presulfurization and process control are all very important.
The prior art hydrogenation catalyst presulfurizing method mainly comprises two classes: the outer presulfurization of presulfurization and device in the device.Presulfurization is that catalyst is loaded into reactor in the device, introduces vulcanizing agent then and vulcanizes, and this is the method that often adopts, and its weak point mainly is that the time is longer, influences the production efficiency of process units.Before the outer presulfurization of catalyst device was meant filling, catalyst had cured or vulcanizing agent exists, and need not to introduce the method for vulcanizing agent after being loaded in the reactor.The major advantage of the outer presulfurization of device is that device is short on-stream time, improves the production efficiency of device.
The outer pre-curing technology of device is to change the metal on the catalyst into metal sulfide fully, and passivation is used then; Or catalyst adds vulcanizing agent before being loaded into reactor, in reactor reactive metal is converted into sulphided state then.Although this method preparation, storage, transportation and filling are all more or less freely, but the subject matter that exists is that vulcanizing agent is difficult to fully act on catalyst metals, the pre-sulfide catalyst of Containing Sulfur agent is packed in the activation process behind the reactor, cause that easily vulcanizing agent runs off and heat release is concentrated in reaction.
The vulcanizing agent that the outer presulfurization of hydrogenating catalyst is selected generally comprises elementary sulfur, organic sulfur compound, inorganic sulphide and said mixture, and adding mode and processing method are had nothing in common with each other, and its presulfurization effect is also had nothing in common with each other.Because the elementary sulfur cost is low, utilization rate is high, many technology use elementary sulfur to be vulcanizing agent.When using elementary sulfur, the mode of in the prior art elementary sulfur being introduced catalyst generally comprises distillation absorption, fusing dipping, is dispersed in dipping in the organic solution, directly uses solid state component sulphur powder etc.
USP4943547, USP5215954 etc. with elementary sulfur join generate in advance in higher boiling oil or the organic solvent suspension again with the fresh catalyst effect, or contact the back with fresh catalyst at the powdery elementary sulfur and soak into higher boiling oil or organic solvent.Said method can reach certain hold sulphur rate, but concentrates the problem of heat release when existing catalyst to activate in reactor, and hold sulphur rate also needs further to improve.USP6077803 is dissolved in elementary sulfur and organic sulfur in the solvent, simultaneously under the condition that stabilizing agent organic acid, mercaptan or organic alcohols exist, be under the stabilizing agent condition particularly, element sulphur is introduced catalyst, but the time still there is concentrated exothermic phenomenon in the weak point activation at glycerine or hexose.
USP5786293, USP5821191, EP352851 etc., generally adopt elementary sulfur is dissolved in (NH as vulcanizing agent with inorganic polymeric form sulfide
3)
2Preparation method in the S solution, its main deficiency is a complicated operation, needs double-steeping just can reach certain last sulfur content at least, and last drying must be carried out in inert atmosphere.
Patents such as USP5017535, EP 329499, USP4725569, EP130850 use the organic sulfur compound of mercaptan, dimethylsulphide, carbon disulfide and other carbon atoms 1-20 as vulcanizing agent.USP5922638, USP5397756 etc. use elementary sulfur and organic sulfur jointly as vulcanizing agent.Subject matter with organic sulfurizing agent is that consumption is big, the price height, and also there are certain problem in transportation and filling process.
CN1107539C contacts with catalyst with hydrocarbon compound earlier, carries out the outer presulfurization of device with hydrogen and sulfur-containing compound then.Owing to there is hydrogen to exist and higher temperature (embodiment is 330 ℃), sulfide decomposes generation hydrogen sulfide (in fact this patent is directly used hydrogen sulfide), metal reaction on hydrogen sulfide and the catalyst generates metal sulfide, this belongs to the method with the complete presulfurization of catalyst, the pre-sulfide catalyst that obtains is easy to spontaneous combustion, existing problems aspect storage, transportation and filling.CN1400056A applies the pre-sulfide catalyst that contains vulcanizing agent at least with the oxygen-bearing organic matter that contains 16 carbon atoms, handling a period of time more than 175 ℃, activate with hydrogen then, to reduce the heating certainly of catalyst, but can not solve fully the sulphided state catalyst from heating problems, still there are certain problem in the storage of catalyst, transportation and filling etc.USP6059956 (CN1076635C) exists down with containing alkene or olefine fraction component such as vegetable oil, elementary sulfur and organic polysulfide are introduced catalyst, activate with hydrogen then, use the oxygen-containing gas passivation at last, though this method can improve catalyst activity, but, still there is above-mentioned identical problem because metal is a sulphided state on the catalyst.
Summary of the invention
At the deficiencies in the prior art, the invention provides a kind of outer presulfurization hydrogenization catalyst preparation method of device that heat release is even, hold sulphur rate is high that activates.
Processing method before hydrogenation catalyst of the present invention is used, i.e. the method for load vulcanizing agent before hydrogenation catalyst uses, detailed process comprises the steps:
(1) gets the oxidation state hydrogenation catalyst;
(2) the oxidation state hydrogenation catalyst is introduced organic solvent and elementary sulfur (being elemental sulfur), and the addition of elementary sulfur is theoretical 30%～150% of the sulfur content that needs of hydrogenation catalyst, is preferably 70%～120%, and most preferably 80%～105%.Hydrogenation catalyst is theoretical need sulfur content to be that institute's metallic components is converted into sulfide (Co on the catalyst
9S
8, MoS
2, Ni
3S
2, WS
2) time need the amount of sulphur.The organic solvent use amount is 0.1%～50% of a catalyst weight, and is preferred 2%～50%, more preferably 5%～30%;
(3) hydrogenation catalyst that contains organic solvent and sulphur that step (2) is obtained is handled by following process: processing 0～20h under 100～130 ℃ (hour), preferred 0.2～15h, handle 0.2～15h down at 130～180 ℃, handle 0～15h down at 180～300 ℃, preferred 1～8h promptly obtains Containing Sulfur agent hydrogenation catalyst.
In the above-mentioned steps (1), the hydrogenation catalyst of oxidation state can be conventional hydrogenation catalyst, as Hydrobon catalyst, hydrotreating catalyst, hydrocracking catalyst etc.It generally is carrier with the refractory inorganic oxides, as the composite oxides of aluminium oxide, silica, amorphous silicon aluminium, titanium oxide, molecular sieve and each several element or mix the carrier of oxygen etc., active metal component is generally one or more among W, Mo, Ni and the Co, can contain auxiliary agent simultaneously.The selection of catalyst carrier for hydrgenating, active metal component and auxiliary agent and consumption can specifically be determined according to the needs of using according to this area general knowledge.
Organic solvent described in the step (2) can adopt some commonly used organic solvents of this area, as in hydrocarbon ils and the organic carboxylic ester one or more.Hydrocarbon ils generally can be from the heavy end wet goods of various naphthas, gasoline, kerosene, diesel oil, white oil, lam-oil, lube base oil, straight run and decompression one or more, the hydrocarbon ils that obtains of secondary operations preferably, the above-mentioned hydrocarbon ils that obtains as technologies such as catalytic cracking, thermal cracking.Organic carboxylic ester can be the organic carboxylic ester that contains 6～60 carbon atoms, the preferred fat acid glyceride, as sesame oil, safflower seed oil, corn oil, cottonseed oil, peanut oil, rapeseed oil, soya-bean oil, walnut oil, coconut oil, olive oil, sunflower oil, lard, n-butyl acetate, 1-Methoxy-2-propyl acetate, 1, the 4-butanediol diacrylate, the cyclohexylenedinitrilotetraacetic acid isopropyl ester, hexa-methylene-1,6 vulcabond, triethyl phosphate, methyl phenylacetate, isobutyl phenylacetate, the terephthalic acid (TPA) dinonyl, repefral, diethyl phthalate, Methyl Salicylate, butyl p-hydroxybenzoate, and in similar other organic carboxylic ester etc. one or more.Hydrocarbon ils, organic carboxylic ester can be used alone, but also also mix together, and use its weight ratio can be 1: 10～10: 1 (hydrocarbon ils: organic carboxylic ester) if mix.The preferred mixing uses, and can more help solving the heat release problem of concentrating.Can add an amount of sulfurous organic compound in the organic solvent, as sulfone class material, thio-alcohol material, thiurams material, organic polysulfide etc. one or more, consumption is generally 0.01%～1% of catalyst weight.
The organic solvent in the step (2) and the carrying method of elementary sulfur can adopt in the prior art any mode as: (1) elementary sulfur loads to earlier on the catalyst, floods organic solvent then; (2) elementary sulfur is dispersed in the organic solvent, is incorporated on the catalyst jointly then; (3) earlier organic solvent is impregnated on the catalyst, introduces elementary sulfur then; (4) earlier organic solvent is impregnated on the catalyst, mixes with the elementary sulfur pressed powder then.
Before or after step (2), can load organic acid and/or organonitrogen compound class material on the hydrogenation catalyst, preferred organonitrogen compound class material, organic acid and/or organonitrogen compound class material load capacity are 0.5%～20% of catalyst weight, are preferably 2.0%～10%.Also above-mentioned organic acid and/or organonitrogen compound class material directly can be mixed with the organic solvent of use in the step (2), be incorporated in the hydrogenation catalyst jointly.Organic acid and/or organonitrogen compound are introduced the concrete mode of hydrogenation catalyst and can be determined by this area general knowledge according to the character of selected species, material for example soluble in water can be made into the aqueous solution, the material that is soluble in organic solvent can be made into organic solution, and the material that boiling point is lower can directly be introduced etc.Organic sulfur compound also can be incorporated on the catalyst simultaneously with organic acid or organonitrogen compound class material, or is introduced separately on the catalyst before or after introducing elementary sulfur.Described organic acid can be the organic carboxyl acid that contains 2～25 carbon atoms, the organic carboxyl acid that preferably contains 4～18 carbon atoms, can be that monoacid also can be binary acid, ternary acid etc., as acetate, ethanedioic acid, ethylenediamine tetra-acetic acid, n-nonanoic acid, citric acid, salicylic acid, malic acid, laurate, butanedioic acid, tartaric acid, vinyl acetate, butadiene acid, grape acid, Fructus Hordei Germinatus acid, oleic acid, linoleic acid, stearic acid, palmitic acid, lactic acid, 12-hydroxy stearic acid, 3,4, one or more in the 5-trimethoxybenzoic acid etc.The organonitrogen compound that uses can be the organonitrogen compound that contains 1～15 carbon atom, the organonitrogen compound that preferably contains 2～10 carbon atoms, as the alkyl amine substance, the alcamines material, the amino acids material, organic ammonium salt material, in the amide substance etc. one or more, concrete material such as ethylenediamine, monoethanolamine, diethanol amine, triethanolamine, diisopropanolamine (DIPA), triethylamine, the 2-cyclohexanediamine, 1, the 3-propane diamine, triethylene diamine, triethylene tetramine, tert-butylamine, lauryl amine, trioctylamine, three isopropyl acid ammoniums, N, the N-diethyl ethylene diamine, amino-nonanoic acid, amion acetic acid, complexon I, N, the N-diethyl hydroxylamine, N methyldiethanol amine, the ethanedioic acid ammonium, hexa, ammonium dimethyl-dithiocarbamate, N, the N-diisopropyl ethanolamine, phosphoamide, antifebrin, N, N-dihydroxy ethyl aniline, thiocarbamide, semicarbazides, glutamic acid, rhodan ammonium, and in other material close one or more with the above-mentioned substance structure.The preferred organic matter that contains nitrogen and oxygen simultaneously.Organic acid and organonitrogen compound can be used alone, but also also mix together, and mixed proportion without limits.The carrying method of organic acid and/or organonitrogen compound can adopt infusion process, can directly organonitrogen compound and/or organic acid be introduced on the hydrogenation catalyst, also organic acid and/or organonitrogen compound can be mixed with the aqueous solution, ammonia spirit or organic solution, flood hydrogenation catalyst then, the hydrogenation catalyst that drying is removed and to be anhydrated, ammoniacal liquor or organic solvent obtain load organic acid and/or organonitrogen compound.Ammonia concn generally need not limit, and can dissolve selected material smoothly and get final product, and general weight concentration is 0.1%～25%.Organic solvent generally is the organic solvent of the solubilized above-mentioned substance of boiling point lower (as being lower than 100 ℃), as ethanol, methyl alcohol, ether, benzene, carbon tetrachloride etc., can select to determine by this area general knowledge according to the organic matter of need dissolving.Dry condition is in 80 ℃～200 ℃ oven dry of temperature, preferably between 80 ℃～140 ℃, is controlled at 1～20 hour preferred 2～8 hours drying time.Latter's carrying method is easier to make organic acid and/or organonitrogen compound to be dispersed on the hydrogenation catalyst, is preferred scheme.Also can add the sulfur-containing compound that dissolves in above-mentioned substance or solution in right amount simultaneously, as ammonium sulfide etc., its consumption is generally 0.01%～1% of catalyst weight.
Can adopt absolute pressure during the heat pre-treatment of step (3) is 0.05～1MPa pressure condition, generally can carry out under normal pressure.Heat pre-treatment can be an inert gas environment, also can be that oxygen content is flowing of 0.1v%～30v% or non-current atmosphere, but generally not need forced flow atmosphere, adopts do not flow atmosphere or the spontaneous current atmosphere of taking offence to get final product.
In the outer presulfurization processing procedure of hydrogenating catalyst of the present invention, be main vulcanizing agent, have the low advantage of cost with elementary sulfur.After introducing elementary sulfur and organic solvent, under higher temperature, carry out the heat pre-treatment process, can strengthen the active force between elementary sulfur and organic solvent and the hydrogenation catalyst on the one hand, effectively improve the hold sulphur rate of using in the activation process; On the other hand,, emit partial reaction heat, alleviated the concentrated heat release problem in activation process because the heat pre-treatment process can make metal oxide generation partial reaction on elementary sulfur and organic solvent and the hydrogenation catalyst under higher temperature.Particularly adopt segmented heat pre-treatment method of the present invention, can make elementary sulfur and organic solvent and metal oxide under different temperature sections, form the state of different conjugations, the exothermic temperature scope difference of these different material bonding states when activation, the exothermic heat of reaction of catalyst in activation process disperseed in a big way, effectively slow down concentrated exothermic phenomenon, helped the activation and the application of catalyst.In addition, in the outer pre-vulcanization process of hydrogenating catalyst of the present invention, at first at a spot of organic acid of oxidized catalyst area load and/or organonitrogen compound, load elementary sulfur and organic solvent then, carry out heat pre-treatment at last, this further improves the hold sulphur rate of hydrogenation catalyst in activation process that contains vulcanizing agent, has further solved concentrated heat release problem.With solution dipping method load organic acid and/or organonitrogen compound, possible cause is that the material of load distributes more even on catalyst.Experiment shows, adopts the present invention to carry out the catalyst preliminary treatment and helps improving hold sulphur rate and solve concentrated heat release problem, the concentrated heat release problem in the time of particularly can effectively solving the catalyst activation.Wherein use the organic matter that contains oxygen and nitrogen simultaneously to concentrate exothermic phenomenon more favourable to the hold sulphur rate that improves catalyst with slowing down, effect is more outstanding.Adopt the organic solvent of dipping earlier of the present invention during the load elementary sulfur, the method for load elementary sulfur can further solve the low and concentrated exothermic phenomenon of prior art hold sulphur rate then.Preheat processing behind the load vulcanizing agent, can further strengthen the combination of vulcanizing agent and catalyst, also partial reaction may take place, emit the part heat, therefore further solved the sulphur loss when Containing Sulfur agent pre-sulfide catalyst activates and concentrate the heat release problem in reactor.The Containing Sulfur agent hydrogenation catalyst that the inventive method obtains does not have pyrophorisity, is easy to store, transports and uses.
Adopt the present invention to carry out the catalyst preliminary treatment, can fully improve the cure efficiency of catalyst, and then improve the hydrogenation reaction performance of catalyst, as improving hydrodesulfurization activity, the hydrodenitrogenationactivity activity of catalyst, and other are as performances such as hydrogenation are saturated etc.Adopt the present invention to carry out the catalyst preliminary treatment, make the above-mentioned hydrogenation performance that waits of catalyst obviously be better than the catalyst that vulcanization process vulcanizes in the common device.
Description of drawings
Fig. 1 is the embodiment of the invention 2 beds entrance and exit difference curve in Containing Sulfur agent hydrogenation catalyst EPRES-2 when activation of obtaining.
Fig. 2 is the comparative example 1 of the present invention beds entrance and exit difference curve in Containing Sulfur agent hydrogenation catalyst C-EPRES-2 when activation of obtaining.
The specific embodiment
Select existing hydrogenation catalyst to carry out the outer presulfurization of device below and handle, further specify the process and the effect of the inventive method, but do not limit the scope of the invention.
Embodiment 1
Select commercial Hydrobon catalyst FH-5A (Fushun Petrochemical Research Institute's development, Hua Hua group company in Wenzhou produces), main composition and character see Table 1.
Concrete presulfurization processing procedure is as follows:
1, the elementary sulfur of fusing is introduced oxidized catalyst, the introducing amount of elementary sulfur is theoretical 105% of the sulfur content that needs of catalyst.With the fraction of coker gas oil dipping, its consumption is 45% of a catalyst weight then.
2, the catalyst that obtains of step 1 normal pressure, flow of nitrogen gas atmosphere (nitrogen amount 25L/L catalyst hour), 150 ℃ handle 4 hours, 260 ℃ down and handled 2 hours down, finally contained the Hydrobon catalyst EPRES-1 of vulcanizing agent.
Embodiment 2
Oxidized catalyst is identical with embodiment 1, is FH-5A.
Concrete presulfurization processing procedure is as follows:
1, triethylamine is evenly soaked be loaded on the oxidation state FH-5A catalyst, the triethylamine addition is 5% of a catalyst weight, obtains the catalyst of load triethylamine.
2, elementary sulfur being dispersed in catalytically cracked gasoline and rapeseed oil volume ratio is in 8: 1 the solvent, solvent load is 15% of a catalyst weight, the elementary sulfur consumption is theoretical 105% of the sulfur content that needs of catalyst containing metal, has disperseed the solvent of elementary sulfur to spray the catalyst of the load triethylamine that obtains in step 1.
3, the catalyst that obtains of step 2 at normal pressure, moving air atmosphere, 160 ℃ are handled 2 hours, 230 ℃ down and are handled 4, are finally contained the Hydrobon catalyst EPRES-2 of vulcanizing agent.
Comparative example 1
Press the method for embodiment 2, cancelled for the 1st and the 3rd step, the 2nd goes on foot that also embodiment 2 is identical, obtains containing the Hydrobon catalyst C-EPRES-2 of vulcanizing agent.
Embodiment 3
Oxidized catalyst is identical with embodiment 1, is FH-5A.
Concrete presulfurization processing procedure is as follows:
1, triethylamine and grape acid were dissolved in the ammoniacal liquor that contains ammonia 8wt% by weight 4: 1, with this solution impregnation oxidized catalyst, the above-mentioned substance consumption is 15% of a catalyst weight, descends dry 4 hours at 130 ℃ then, obtains containing the catalyst that mixes organics additive.
2, vacuum distillate and peanut oil volume ratio are 1: 2 miscible agent, and solvent load is 0.5% of a catalyst weight, mix with the elementary sulfur pressed powder then, and the elementary sulfur consumption is theoretical 90% of the sulfur content that needs of catalyst containing metal.
3, the material that obtains of step 2 was handled 15 hours for 110 ℃ in normal pressure, moving air atmosphere not, handled 10 hours for 160 ℃, was finally contained the Hydrobon catalyst EPRES-3 of vulcanizing agent.
Embodiment 4
Select commercial Hydrobon catalyst FH-DS (Fushun Petrochemical Research Institute's development, Hua Hua group company in Wenzhou produces), main composition and character see Table 2.
Concrete presulfurization processing procedure is as follows:
1, the amion acetic acid aqueous solution (containing amion acetic acid 2.5wt%) is uniformly impregnated within on the oxidation state FH-DS catalyst, the amion acetic acid addition is 1% of a catalyst weight, 110 ℃ of dryings 3 hours, evaporates moisture then, obtains the catalyst of load amion acetic acid.
2, add oleic acid then, its consumption is 16% of a catalyst weight, mixes with the elementary sulfur pressed powder then, and the use amount of elementary sulfur is theoretical 115% of the sulfur content that needs of catalyst.
3, the material that obtains of step 2 was handled 3 hours for 120 ℃ in normal pressure, moving air atmosphere not, handled 5 hours for 160 ℃, handled 7 hours for 240 ℃, was finally contained the Hydrobon catalyst EPRES-3 of vulcanizing agent.
Embodiment 5
Oxidized catalyst is identical with embodiment 4, is FH-DS.
Concrete presulfurization processing procedure is as follows:
1, butadiene acid, tert-butylamine and phosphoamide were mixed and prepared its aqueous solution by weight 1: 2: 1, with this solution impregnation oxidized catalyst, the above-mentioned substance consumption is 2.7% of a catalyst weight, descends dry 6 hours at 120 ℃ then, obtains containing the catalyst that mixes organics additive.
2, with kerosene and 1,4-butanediol diacrylate volume ratio is the catalyst that 1: 2 impregnation steps (1) obtains, solvent load is 9% of a catalyst weight, mixes with the elementary sulfur pressed powder then, and the elementary sulfur consumption is theoretical 125% of the sulfur content that needs of catalyst containing metal.
3, the material that obtains of step 2 was handled 20 minutes for 115 ℃ in normal pressure, moving air atmosphere not, handled 12 hours for 145 ℃, handled 2 hours down, was finally contained the Hydrobon catalyst EPRES-5 of vulcanizing agent for 270 ℃.
Embodiment 6
Select commercial catalyst for hydroprocessing of heavy oil 3996 (Fushun Petrochemical Research Institute's development, the Fushun Petrochemical Company catalyst plant is produced), main composition and character see Table 3.
Concrete presulfurization processing procedure is as follows:
1, with triethanolamine and N, 2: 1 mixture of N-diethylaminoethanol weight ratio is dissolved in the ammoniacal liquor that contains ammonia 5wt%, contains ammonium sulfide in the solution, and the ammonium sulfide consumption accounts for 2.0% of catalyst weight.With this solution impregnation oxidized catalyst, above-mentioned organonitrogen compound consumption is 2.5% of a catalyst weight, descends dry 4 hours at 150 ℃ then, obtains containing the catalyst that mixes organonitrogen compound.
2, the catalyst that contains organic nitrogen compound that obtains with peanut oil and 3: 1 mixed ester impregnation steps 1 of lard weight ratio, the consumption of mixed ester is 25% of a catalyst weight, in closed container the elementary sulfur that distils is incorporated on the catalyst then, the consumption of elementary sulfur is theoretical 45% of the sulfur content that needs of catalyst metals.
3, the catalyst that obtains of step 2 is at absolute pressure 0.08MPa, and the air atmosphere of Liu Donging was handled 30 minutes for 140 ℃ naturally, handles 4 hours down, is finally contained the hydrotreating catalyst EPRES-6 of vulcanizing agent for 260 ℃.
Embodiment 7
Use embodiment 6 described heavy oil hydrogenating treatment catalysts.
Concrete presulfurization processing procedure is as follows:
1, triethylene diamine is dissolved in the ethanol, weight concentration is 20%, sprays oxidized catalyst with this solution, and the triethylene diamine consumption is 7% of a catalyst weight, evaporates 3 hours down at 175 ℃ then, obtains containing the catalyst of triethylene diamine.
2, the catalyst that obtains with peanut oil and 8: 1 mixed solvent impregnation steps 1 of No. 150 lubricating base oils weight ratios, the consumption of mixed solvent is 10% of a catalyst weight, contain tetramethylthiuram disulfide in the mixed solvent, consumption is 0.2% of a catalyst weight.Then the elementary sulfur pressed powder is mixed, the consumption of elementary sulfur is theoretical 110% of the sulfur content that needs of catalyst metals.
3, material nitrogen atmosphere in closed container of obtaining of step 2, absolute pressure 0.5MPa handled 15 hours down for 125 ℃, handled 1 hour down at 155 ℃, handled 12 hours down at 210 ℃, was finally contained the hydrotreating catalyst EPRES-7 of vulcanizing agent.
Embodiment 8
Commercial hydrocracking catalyst 3974 (Fushun Petrochemical Research Institute's development, the Fushun Petrochemical Company catalyst plant produces), main character sees Table 4.
Concrete presulfurization processing procedure is as follows:
1, linoleic acid mixes with catalytic cracking diesel oil, and oxide impregnation attitude catalyst, linoleic consumption are 7% of catalyst weight, and the catalytic cracking diesel oil consumption is 2% of a catalyst weight.
2, the catalyst that obtains of step (1) mixes with the elementary sulfur pressed powder, and the consumption of elementary sulfur is theoretical 105% of the sulfur content that needs of catalyst metals.
3, the catalyst that obtains of step 2 is the atmosphere that do not flow of 2v% in normal pressure, oxygen content, handled 2 hours down for 110 ℃, handled 1 hour down, handled 2 hours down at 190 ℃ at 150 ℃, handled 3 hours down at 240 ℃, finally contained the hydrocracking catalyst EPRES-8 of vulcanizing agent.
The hydrogenation catalyst of the Containing Sulfur agent that the various embodiments described above and comparative example obtain carries out hold sulphur rate and activation processing.The hold sulphur rate test condition is: pressure 5.5MPa, 155 ℃ of temperature, H
2/ diesel oil (character sees Table 6) volume ratio is 400, and volume space velocity is 4.0h during liquid
-1, constant temperature 6 hours.Hold sulphur rate is for accounting for the percentage by weight of initial sulphur through the sulphur that keeps after the above-mentioned processing.Concrete outcome sees Table 5.
Each embodiment and comparative example obtain Containing Sulfur agent hydrogenation catalyst activation processing process and condition is: carry out in fixed bed reactors, the catalyst bed layer height is 800mm, pressure 5.5MPa, volume space velocity 2.5h during diesel oil (character sees Table 5) liquid
-1, H
2/ diesel oil volume ratio 600: 1,110 ℃ begin into diesel oil, with 27 ℃/h of average heating speed reactor inlet temperature are risen to 340 ℃ (temperature-rise period inlet temperatures control can referring to Fig. 1), and 340 ℃ of constant temperature 8 hours, activation finished then.The bed outlet the results are shown in Table 7 with the inlet maximum temperature rise in each sulfur-bearing catalyst activation process.Catalyst EPRES-2 temperature-rise period entrance and exit temperature curve is seen Fig. 1, and comparative example catalyst C-EPRES-2 temperature-rise period entrance and exit temperature curve is seen Fig. 2.
Effect contrast when EPRES-2 and C-EPRES-2 are used for diesel oil fraction hydrogenating sees Table 8.
Table 1 FH-5A Hydrobon catalyst is mainly formed and character
| Catalyst | Oxidation state FH-5A |
| Carrier | γ-Al 2O 3 |
| Reactive metal composition/wt% | |
| MoO 3 | 24.3 |
| NiO | 4.2 |
| Auxiliary agent SiO 2/wt％ | 10.1 |
| Pore volume/mlg -1 | 0.4 |
| Specific area/m 2·g -1 | 190 |
Table 2 FH-DS Hydrobon catalyst is mainly formed and character
| Catalyst | Oxidation state FH-DS |
| Carrier | γ-Al 2O 3 |
| Reactive metal composition/wt% | |
| WO 3 | 19.3 |
| MoO 3 | 6.7 |
| NiO | 2.2 |
| CoO | 3.4 |
| Pore volume/mlg -1 | 0.32 |
| Specific area/m 2·g -1 | 170 |
Table 3 heavy oil hydrogenating treatment catalyst 3996 main composition and character
| Catalyst | Oxidation state 3996 |
| Carrier | γ-Al 2O 3 |
| Reactive metal composition/wt% | |
| MoO 3 | 23.9 |
| NiO | 4.2 |
| Auxiliary agent P 2O 5/wt％ | 3.8 |
| Pore volume/mlg -1 | 0.35 |
| Specific area/m 2·g -1 | 173 |
Table 4 hydrocracking catalyst 3974 main character and composition
| Catalyst | Oxidation state 3974 |
| Carrier/wt% | |
| γ-Al 2O 3 | Surplus |
| Amorphous silicon aluminium (SiO 2Weight content 40%) | 35 |
| Modified Y molecular sieve (SiO 2/Al 2O 3Mol ratio 13) | 15 |
| Reactive metal composition/wt% | |
| WO 3 | 28.2 |
| NiO | 4.2 |
| Pore volume/mlg -1 | 0.40 |
| Specific area/m 2·g -1 | 240 |
Table 5 embodiment and comparative example Containing Sulfur agent hydrogenation catalyst hold sulphur rate
| Sequence number | Contain sulfur catalyst | Hold sulphur rate, % |
| Embodiment 1 | EPRES-1 | 63.1 |
| Embodiment 2 | EPRES-2 | 75.7 |
| Comparative example 1 | C-EPRES-2 | 53.2 |
| Embodiment 3 | EPRES-3 | 77.8 |
| Embodiment 4 | EPRES-4 | 74.7 |
| Embodiment 5 | EPRES-5 | 71.9 |
| Embodiment 6 | EPRES-6 | 79.4 |
| Embodiment 7 | EPRES-7 | 72.5 |
| Embodiment 8 | EPRES-8 | 73.4 |
Test of table 6 hold sulphur rate and activation process diesel oil character
| Feedstock oil | Diesel oil |
| Density (20 ℃)/kgm -3 | 0.8305 |
| The end point of distillation/℃ | 352 |
| Sulphur/μ gg -1 | 687 |
| Nitrogen/μ gg -1 | 116.7 |
| Acidity/mgKOH (100mL) -1 | 5.53 |
Bed maximum temperature rise when table 7 embodiment and the activation of comparative example Containing Sulfur agent hydrogenation catalyst
| Sequence number | Contain sulfur catalyst | Maximum bed temperature rise during activation, ℃ |
| Embodiment 1 | EPRES-1 | 11 |
| Embodiment 2 | EPRES-2 | 9 |
| Comparative example 1 | C-EPRES-2 | 24 |
| Embodiment 3 | EPRES-3 | 8 |
| Embodiment 4 | EPRES-4 | 10 |
| Embodiment 5 | EPRES-5 | 12 |
| Embodiment 6 | EPRES-6 | 7 |
| Embodiment 7 | EPRES-7 | 11 |
| Embodiment 8 | EPRES-8 | 12 |
Table 8 EPRES-2 and C-EPRES-2 are used for the condition and the effect of diesel oil fraction hydrogenating
| The catalyst title | EPRES-2 | C-EPRES-2 | |
| Raw material and product | Catalytic cracking diesel oil | Refined oil | |
| Reaction temperature/℃ | 340 | 340 | |
| Reaction pressure/MPa | 6.0 | 6.0 | |
| Hydrogen-oil ratio | 350 | 350 | |
| Volume space velocity/h -1 | 3.0 | 3.0 | |
| Density (20 ℃)/kgm -3 | 0.9334 | 0.9431 | 0.9459 |
| The end point of distillation/℃ | 355 | 354 | 353 |
| Sulphur/μ gg -1 | 10766 | 1125 | 3274 |
| Nitrogen/μ gg -1 | 767 | 81.2 | 125.4 |
Claims (18)
1, the processing method before a kind of hydrogenation catalyst is used comprises the steps:
(1) gets the oxidation state hydrogenation catalyst;
(2) the oxidation state hydrogenation catalyst is introduced organic solvent and elementary sulfur, and the addition of elementary sulfur is theoretical 30%～150% of the sulfur content that needs of hydrogenation catalyst, and the organic solvent use amount is 0.1%～50% of a catalyst weight;
(3) hydrogenation catalyst that contains organic solvent and sulphur that step (2) is obtained was handled 0～20 hour down at 100～130 ℃, handled 0.2～15 hour down at 130～180 ℃, handled 0～15 hour down at 180～300 ℃.
2, in accordance with the method for claim 1, it is characterized in that the described processing procedure of step (3) is: be to carry out under the condition of 0.1v%～30v% in inert gas environment or oxygen content.
3,, it is characterized in that it is 0.05～3MPa pressure condition that the described processing procedure of step (3) adopts absolute pressure according to claim 1 or 2 described methods.
4, in accordance with the method for claim 1, the addition that it is characterized in that the elementary sulfur described in the step (2) is theoretical 70%～120% of the sulfur content that needs of hydrogenation catalyst, and the organic solvent use amount is 2%～50% of a catalyst weight.
5, in accordance with the method for claim 1, the addition that it is characterized in that the described elementary sulfur of step (2) is theoretical 80%～105% of the sulfur content that needs of hydrogenation catalyst, and the organic solvent use amount is 5%～30% of a catalyst weight.
6, in accordance with the method for claim 1, it is characterized in that the organic solvent described in the step (2) adopts one or more in hydrocarbon ils and the organic carboxylic ester.
7, in accordance with the method for claim 6, it is characterized in that described hydrocarbon ils is from the heavy end wet goods of naphtha, gasoline, kerosene, diesel oil, white oil, lam-oil, lube base oil, straight run and decompression one or more; Described organic carboxylic ester is the organic carboxylic ester that contains 6～60 carbon atoms.
8, in accordance with the method for claim 6, it is characterized in that described hydrocarbon ils and organic carboxylic ester mix use, hydrocarbon ils: the mixed weight ratio of organic carboxylic ester is 1: 10～10: 1.
9, in accordance with the method for claim 1, it is characterized in that in the described organic solvent adding sulfone class material, thio-alcohol material, thiurams material, organic polysulfide one or more, consumption is 0.01%～1% of a catalyst weight.
10, in accordance with the method for claim 1, one of mode below the carrying method that it is characterized in that organic solvent in the step (2) and elementary sulfur adopts: (1) elementary sulfur loads to earlier on the catalyst, floods organic solvent then; (2) elementary sulfur is dispersed in the organic solvent, is incorporated on the catalyst jointly then; (3) earlier organic solvent is impregnated on the catalyst, introduces elementary sulfur then; (4) earlier organic solvent is impregnated on the catalyst, mixes with the elementary sulfur pressed powder then.
11, in accordance with the method for claim 1, it is characterized in that before or after step (2), can load organic acid and/or organonitrogen compound class material on the hydrogenation catalyst, or organic acid and/or organonitrogen compound class material directly mixed with the organic solvent of use in the step (2), be incorporated into jointly in the hydrogenation catalyst, the load capacity of organic acid and/or organonitrogen compound is 0.5%～20% of a catalyst weight.
12, in accordance with the method for claim 11, the load capacity that it is characterized in that described organic acid and/or organonitrogen compound is 2.0%～10% of a catalyst weight.
13, according to claim 11 or 12 described methods, it is characterized in that described organic acid is the organic carboxyl acid that contains 2～25 carbon atoms, described organonitrogen compound is to contain in 1～15 carbon atom alkyl amine substance, alcamines material, amino acids material, organic ammonium salt material and the amide substance one or more.
14, in accordance with the method for claim 13, it is characterized in that described organic acid is the organic carboxyl acid that contains 4～18 carbon atoms, described organonitrogen compound is the organonitrogen compound that contains 2～10 carbon atoms.
15, in accordance with the method for claim 11, it is characterized in that the carrying method of organic organic acid and/or organonitrogen compound adopts infusion process, or directly organonitrogen compound and/or organic acid are introduced on the hydrogenation catalyst; Wherein infusion process is that organic acid and/or organonitrogen compound are mixed with the aqueous solution, ammonia spirit or organic solution, flood hydrogenation catalyst then, the hydrogenation catalyst that drying is removed and to be anhydrated, ammoniacal liquor or organic solvent obtain load organic acid and/or organonitrogen compound.
16, in accordance with the method for claim 15, it is characterized in that in described infusion process load organic acid and/or the organonitrogen compound process that baking temperature is 80 ℃～200 ℃, be 1～20 hour drying time.
17, in accordance with the method for claim 15, it is characterized in that in the process of organic acid and/or organonitrogen compound load, add dissolve in the sulfur-containing compound of the material that uses or solution, its consumption is 0.01%～1% of a catalyst weight.
18, in accordance with the method for claim 1, it is characterized in that the hydrogenation catalyst of the described oxidation state of step (1) is carrier with the refractory inorganic oxides, active metal component is generally one or more among W, Mo, Ni and the Co.
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