CN101417245A - The processing method of hydrogenation catalyst - Google Patents
The processing method of hydrogenation catalyst Download PDFInfo
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- CN101417245A CN101417245A CNA200710157782XA CN200710157782A CN101417245A CN 101417245 A CN101417245 A CN 101417245A CN A200710157782X A CNA200710157782X A CN A200710157782XA CN 200710157782 A CN200710157782 A CN 200710157782A CN 101417245 A CN101417245 A CN 101417245A
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Abstract
The present invention relates to a kind of processing method of hydrogenation catalyst.Detailed process is with behind the catalyst carrier impregnated catalyst active metal component, is dried to certain water content, introduces organic solvent and elemental sulfur then, carries out heat pre-treatment at last under certain condition.Processing method before hydrogenation catalyst of the present invention is used loads to sulphur-containing substance such as elemental sulfur on the hydrogenation catalyst, and has certain interaction, and emit less heat, the water that contains in the catalyst produces steam in heat treatment process, regulate the interaction of sulphur and catalyst activity component, and reduce the heat release degree of heat treatment process.Compared with prior art, the catalyst that obtains of the inventive method has sulphur-containing substance utilization rate height, reaction bed temperature raise mild and the high characteristics of catalyst activity when using activation.The inventive method can be used for the processing procedure before various hydrogenation catalysts are used.
Description
Technical field
The present invention relates to a kind of processing method of hydrogenation catalyst, particularly before catalyst is used for hydrogenation reaction, introduce the processing method of elemental 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 elemental 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 elemental sulfur cost is low, utilization rate is high, many technology use elemental sulfur to be vulcanizing agent.When using elemental sulfur, the mode of in the prior art elemental sulfur being introduced catalyst generally comprises distillation absorption, fusing dipping, is dispersed in dipping in the organic solution, directly uses solid elemental sulfur powder etc.
USP4943547, USP5215954 etc. with elemental 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 elemental 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 elemental 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 elemental 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 elemental 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, elemental 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 processing method of hydrogenating catalyst that heat release is even, hold sulphur rate is high that activates.
The processing method of hydrogenation catalyst of the present invention, i.e. the method for load vulcanizing agent before hydrogenation catalyst uses, detailed process comprises following content:
(1) get catalyst carrier for hydrgenating, with infusion process supported active hydrogenation component, being dried to moisture in stem-based catalyst weight then is 0.1%～30%, is preferably 0.5%～20%, most preferably is 1%～10%.
(2) the oxidation state hydrogenation catalyst is introduced organic solvent and elemental sulfur, and the addition of elemental 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 carries out heat treated, heat-treatment process be 100 ℃～300 ℃ handle down 1～24h (hour), preferably handled 2～12 hours down at 110～200 ℃, most preferably handle: handle 0～20h down at 100～130 ℃ by following process, preferred 0.2～15h handles 0.2～15h down at 130～180 ℃, handles 0～15h down at 180～300 ℃, preferred 1～8h promptly obtains Containing Sulfur agent hydrogenation catalyst.
In the above-mentioned steps (1), hydrogenation catalyst can be conventional hydrogenation catalyst, as Hydrobon catalyst, hydrotreating catalyst, hydrocracking catalyst etc.Catalyst carrier for hydrgenating is generally 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.Infusion process is this area conventional method, and with required active metal component wiring solution-forming, dipping solution contacts with catalyst carrier, and is dry then, but the reserve part water yield.Drying condition is 20～120 ℃ of dryings 0.5～72 hour, is dried to till the required water content.
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 1:20～20:1 (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.
Organic solvent in the step (2) and the load of elemental sulfur order can be any, can be by existing scheme load.As being that two kinds of materials load to respectively on the oxidized catalyst, also two kinds of materials wherein can being mixed the back and load on the oxidized catalyst.One of preferred following several mode of loadings: (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.
In step (2) before, 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 elemental 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, 2-cyclohexanediamine, 1,3-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, drying is removed and to be anhydrated, ammoniacal liquor or organic solvent obtain the hydrogenation catalyst of load organic acid and/or organonitrogen compound, but should be by the required water yield of aforementioned reservation.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.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 treated of step (3) is 0.05～3MPa pressure condition, generally can carry out under normal pressure.In the heat-treatment process, the water that keeps in the catalyst soakage process is evaporated to water vapour, and heat treatment process is carried out under water vapour atmosphere.
In the outer presulfurization processing procedure of hydrogenating catalyst of the present invention, be main vulcanizing agent, have the low advantage of cost with elemental sulfur.Keep suitable quantity of water in the catalyst preparation process, the water that is kept can improve the interaction of elemental sulfur and catalyst metal components in pre-vulcanization process, reduces the sulphur number of dropouts, improves the catalyst serviceability.In heat treatment process, water is evaporated to water vapour, helps absorbing sulphur and metal component reaction liberated heat in the heat treatment process on the one hand, makes the heat treatment process temperature rise less, is easy to control; When presulfurization is handled outside carrying out device on the other hand, because the existence of water vapour, can reduce or avoid contacting of sulphur-containing substance and air, also just reduced the generation (reaction of sulphur and oxygen reaction generation sulfur dioxide of side reaction, this is exothermic reaction), so both can improve the utilization rate of sulphur, reduce the loss of elemental sulfur, simultaneously can reduce intrasystem heat release again, processing safety improves greatly, and discharging exhaust pollutant content significantly reduces (concentration of sulfur dioxide can be up to 10000 μ g/g in the tail gas during operation under air atmosphere), is easier to handle, and disposal cost reduces greatly.
Adopt segmented heat pre-treatment method, can make elemental 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 elemental 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 elemental sulfur, the method for load elemental 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.
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
Composition by commercial Hydrobon catalyst FH-5A (Fushun Petrochemical Research Institute development, Hua Hua group company in Wenzhou produce) prepares catalyst, and catalyst is mainly formed with character and seen Table 1.
Concrete presulfurization processing procedure is as follows:
1, after catalyst carrier and the reactive metal solution impregnation, 80 ℃ of dryings 2 hours, desciccate was in catalyst butt weight moisture 25%.
2, the catalyst mix that elemental sulfur powder and step 1 are obtained, the introducing amount of elemental sulfur are theoretical 105% of the sulfur content that needs of catalyst.Mix with fraction of coker gas oil then, the fraction of coker gas oil consumption is 45% of a catalyst weight.
3, the catalyst that obtains of step 2 was handled 5 hours down normal pressure, 150 ℃, was 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, after catalyst carrier and the reactive metal solution impregnation, 50 ℃ of dryings 8 hours, desciccate was in catalyst butt weight moisture 10%.
2, triethylamine is evenly soaked be loaded on the catalyst that step 1 obtains, the triethylamine addition is 5% of a catalyst weight, obtains the aqueous catalyst of load triethylamine.
3, elemental sulfur powder, organic solvent (organic solvent is that catalytically cracked gasoline and rapeseed oil volume ratio are the mixture of 8:1) are mixed, consumption of organic solvent is 15% of a catalyst weight, the elemental sulfur consumption is theoretical 105% of sulfur content, the catalyst mix of the load triethylamine that said mixture and step 1 obtain of needing of catalyst containing metal.
4, the catalyst that obtains of step 3 was handled 8 hours down 0.3MPa, 160 ℃, was finally contained the Hydrobon catalyst EPRES-2 of vulcanizing agent.
Comparative example
Press the method for embodiment 2, just do not use for the 1st step, catalyst is a commercial catalyst, obtains containing the Hydrobon catalyst C-EPRES-2 of vulcanizing agent.In embodiment 2 heat treatment processes, material has 13 ℃ of temperature rises.In the comparative example, the temperature rise of heat treatment process material is 52 ℃.And the catalyst of embodiment 2 has more outstanding activity.
Embodiment 3
Oxidized catalyst is identical with embodiment 1, is FH-5A.
Concrete presulfurization processing procedure is as follows:
1, after catalyst carrier and the reactive metal solution impregnation, 110 ℃ of dryings 3 hours, desciccate was in catalyst butt weight moisture 0.2%.
2, triethylamine and grape acid are sprayed in the catalyst that step 1 obtains by weight 4:1, obtain containing the catalyst that mixes organics additive.
3, vacuum distillate and peanut oil volume ratio are the mixed solvent of 1:2, solvent load is 0.5% of a catalyst weight, in the mixed solvent catalyst that introducing step 2 obtains earlier, mix with the elemental sulfur pressed powder then, the elemental sulfur consumption is theoretical 90% of the sulfur content that needs of catalyst containing metal.
4, the material that obtains of step 3 was handled 15 hours normal pressure, 105 ℃, handled 10 hours for 160 ℃, was finally contained the Hydrobon catalyst EPRES-3 of vulcanizing agent.
Embodiment 4
Composition by commercial Hydrobon catalyst FH-DS (Fushun Petrochemical Research Institute development, Hua Hua group company in Wenzhou produce) adopts immersion process for preparing, and commercial catalyst is mainly formed with character and seen Table 2.
Concrete presulfurization processing procedure is as follows:
1, after catalyst carrier and the reactive metal solution impregnation, 100 ℃ of dryings 2 hours, desciccate was in catalyst butt weight moisture 7%.
2, amion acetic acid is uniformly impregnated within on the catalyst of step 1, the amion acetic acid addition is 1% of a catalyst weight, obtains the catalyst of load amion acetic acid and water.
3, add oleic acid then, its consumption is 16% of a catalyst weight, mixes with the elemental sulfur pressed powder then, and the use amount of elemental sulfur is theoretical 115% of the sulfur content that needs of catalyst.
4, the material that obtains of step 3 was handled 6 hours normal pressure, 120 ℃, handled 2 hours for 170 ℃, handled 5 hours for 240 ℃, was finally contained the Hydrobon catalyst EPRES-4 of vulcanizing agent.
Embodiment 5
Oxidized catalyst is identical with embodiment 4, is FH-DS.
Concrete presulfurization processing procedure is as follows:
1, after catalyst carrier and the reactive metal solution impregnation, 40 ℃ of dryings 48 hours, desciccate was in catalyst butt weight moisture 2%.
2, step 1 catalyst kerosene and 1,4-butanediol diacrylate volume ratio is the mixed solvent dipping of 1:2, solvent load is 9% of a catalyst weight, mixes with the elemental sulfur pressed powder then, and the elemental 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
Composition by commercial catalyst for hydroprocessing of heavy oil 3996 (Fushun Petrochemical Research Institute development, Fushun Petrochemical Company catalyst plant produce) prepares catalyst, and commodity are mainly formed with character and seen Table 3.
Concrete presulfurization processing procedure is as follows:
1, after catalyst carrier and the reactive metal solution impregnation, contain ammonium sulfide in the dipping solution, the ammonium sulfide consumption accounts for 2.0% of catalyst weight, and 70 ℃ of dryings 5 hours, desciccate was in catalyst butt weight moisture 10%.
2, with triethanolamine and N, the catalyst of the impregnation mixture step 1 of N-diethylaminoethanol weight ratio 2:1, above-mentioned organonitrogen compound consumption is 2.5% of a catalyst weight.
3, the organic solvent mixture of peanut oil and lard weight ratio 3:1, the catalyst mix dipping that organic solvent and step 2 obtain, the consumption of mixed organic solvents is 25% of a catalyst weight, with the elemental sulfur powder, the consumption of elemental sulfur is theoretical 45% of the sulfur content that needs of catalyst metals then.
4, the catalyst that obtains of step 3 was handled 30 minutes for 140 ℃ at absolute pressure 0.1MPa, handled 4 hours down, was 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, after catalyst carrier and the reactive metal solution impregnation, 50 ℃ of dryings 15 hours, desciccate was in catalyst butt weight moisture 3%.
2, with the catalyst of triethylene diamine impregnation steps 1, the triethylene diamine consumption is 7% of a catalyst weight.
3, mixed solvent and the elemental sulfur of peanut oil and No. 150 lubricating base oils weight ratio 8:1 are mixed into dispersion suspension, flood with the catalyst mix that this suspension and step 2 obtain, 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, and the consumption of elemental sulfur is theoretical 110% of the sulfur content that needs of catalyst metals.
4, the material that obtains of step 3 was handled 15 hours down for 125 ℃ at absolute pressure 0.5MPa, 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
Composition by commercial hydrocracking catalyst 3974 (Fushun Petrochemical Research Institute's development, the Fushun Petrochemical Company catalyst plant produces) prepares catalyst, and the commercial catalyst main character sees Table 4.
Concrete presulfurization processing procedure is as follows:
1, after catalyst carrier and the reactive metal solution impregnation, 100 ℃ of dryings 4 hours, desciccate was in catalyst butt weight moisture 1%.
2, linoleic acid mixes with catalytic cracking diesel oil, and the catalyst of impregnation steps 1, linoleic consumption are 7% of catalyst weight, and the catalytic cracking diesel oil consumption is 2% of a catalyst weight.
3, the catalyst that obtains of step 2 mixes with the elemental sulfur pressed powder, and the consumption of elemental sulfur is theoretical 105% of the sulfur content that needs of catalyst metals.
4, the catalyst that obtains of step 3 was handled 2 hours down normal pressure, 110 ℃, handled 1 hour down at 150 ℃, handled 2 hours down at 190 ℃, handled 3 hours down at 240 ℃, was 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, and 155 ℃ of temperature, H2/ diesel oil (character sees Table 6) volume ratio is 400, 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 ℃, and then 340 ℃ of constant temperature 8 hours, activation finishes.The bed outlet the results are shown in Table 7 with the inlet maximum temperature rise in each sulfur-bearing catalyst activation process.
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 | 65.8 |
| Embodiment 2 | EPRES-2 | 77.6 |
| Comparative example 1 | C-EPRES-2 | 71.0 |
| Embodiment 3 | EPRES-3 | 81.2 |
| Embodiment 4 | EPRES-4 | 77.0 |
| Embodiment 5 | EPRES-5 | 76.5 |
| Embodiment 6 | EPRES-6 | 83.8 |
| Embodiment 7 | EPRES-7 | 78.5 |
| Embodiment 8 | EPRES-8 | 80.5 |
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 | 9.1 |
| Embodiment 2 | EPRES-2 | 7.2 |
| Comparative example 1 | C-EPRES-2 | 12.0 |
| Embodiment 3 | EPRES-3 | 6.0 |
| Embodiment 4 | EPRES-4 | 8.1 |
| Embodiment 5 | EPRES-5 | 9.2 |
| Embodiment 6 | EPRES-6 | 5.3 |
| Embodiment 7 | EPRES-7 | 8.7 |
| Embodiment 8 | EPRES-8 | 9.5 |
Table 8 EPRES-2 and C-EPRES-2 are used for the condition and the effect of diesel oil fraction hydrogenating
Claims (16)
1, a kind of processing method of hydrogenation catalyst comprises following content:
(1) get catalyst carrier for hydrgenating, with infusion process supported active hydrogenation component, being dried to moisture in stem-based catalyst weight then is 0.1%～30%;
(2) the oxidation state hydrogenation catalyst is introduced organic solvent and elemental sulfur, and the addition of elemental 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 carries out heat treated, and heat-treatment process is to handle 1～24h down at 100 ℃～300 ℃, obtains Containing Sulfur agent hydrogenation catalyst.
2, in accordance with the method for claim 1, it is characterized in that described activity of hydrocatalyst metal component is one or more among W, Mo, Ni and the Co.
3, in accordance with the method for claim 1, it is characterized in that it is 0.5%～20% that the described catalyst of step (1) is dried to moisture in stem-based catalyst weight; The described elemental sulfur addition of 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.
4, in accordance with the method for claim 1, it is characterized in that it is 1%～10% that the described catalyst of step (1) is dried to moisture in stem-based catalyst weight; The described matter sulphur of step (2) addition 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.
5, in accordance with the method for claim 1, it is characterized in that the described heat treated condition of step (3) is for handling 2～12 hours down at 110～200 ℃.
6, in accordance with the method for claim 1, it is characterized in that the described heat treated condition of step (3) is: handle 0～20h down at 100～130 ℃, handle 0.2～15h down, handle 1～8h down at 180～300 ℃ at 130～180 ℃.
7, in accordance with the method for claim 1, it is characterized in that the organic solvent described in the step (2) is one or more in hydrocarbon ils and the organic carboxylic ester, hydrocarbon ils is from the heavy distillate of naphtha, gasoline, kerosene, diesel oil, white oil, lam-oil, lube base oil, straight run and decompression one or more, and organic carboxylic ester is the organic carboxylic ester that contains 6～60 carbon atoms.
8, in accordance with the method for claim 7, it is characterized in that described organic carboxylic ester is selected from 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, in Methyl Salicylate and the butyl p-hydroxybenzoate one or more.
9, in accordance with the method for claim 1, it is characterized in that described organic solvent is a hydrocarbon ils: the organic carboxylic ester weight ratio is the mixture of 1:20～20:1.
10, in accordance with the method for claim 1, it is characterized in that in the step (2) that the load of organic solvent and elemental sulfur is random order in proper order.
11, according to claim 1 or 10 described methods, it is characterized in that the load of described organic solvent and elemental sulfur is one of following manner in proper order: (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.
12, in accordance with the method for claim 1, it is characterized in that before in step (2), load organic acid and/or organonitrogen compound class material on the hydrogenation catalyst, organic acid and/or organonitrogen compound class material load capacity are 0.5%～20% of catalyst weight.
13, in accordance with the method for claim 1, add organic acid and/or organonitrogen compound class material in the organic solvent that it is characterized in that using in the step (2), organic acid and/or organonitrogen compound class material load capacity are 0.5%～20% of catalyst weight.
14, according to claim 12 or 13 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 the organonitrogen compound that contains 1～15 carbon atom.
15, according to claim 12 or 13 described methods, it is characterized in that described organic acid is selected from 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 and 3,4, one or more in the 5-trimethoxybenzoic acid; Described organonitrogen compound is selected from ethylenediamine, monoethanolamine, diethanol amine, triethanolamine, diisopropanolamine (DIPA), triethylamine, 2-cyclohexanediamine, 1,3-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, in glutamic acid and the rhodan ammonium one or more.
16, in accordance with the method for claim 1, it is characterized in that the described catalyst drying condition of step (1) is for 20～120 ℃ of dryings 0.5～72 hour.
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