CN102909027A - Preparation method of catalyst by ultralow-sulfur hydrofining - Google Patents
Preparation method of catalyst by ultralow-sulfur hydrofining Download PDFInfo
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Abstract
The invention relates to a preparation method of catalyst by ultralow-sulfur hydrofining. Al2O3-SiO2-ZrO2 tertiary compound oxide as a carrier, W-Mo-Ni-Co quaternary elements as active metal components and P as aid are used to prepare the catalyst which is butterfly-shaped. The preparation method is characterized by introducing SiO2 to Al2O3 to modulate surface acidity of the carrier and increasing specific surface area and pore volume of the carrier; introducing ZrO2 to increase low-temperature reactivity of the catalyst; preparing metallic co-impregnated solution by complexing process, and loading W-Mo-Ni-Co quaternary active metal components and the aid P by means of stepwise saturated impregnation to increase dispersity and utilization rate of active metals. The catalyst has the advantages of large specific surface, large pore volume, moderate surface acidity, high metal reduction activity and high low-temperature reactivity. Compared with like catalysts, the catalyst can be used to produce ultralow-sulfur diesel with lower than 10microgram/g sulfur content under low reaction severity.
Description
Technical field
The invention belongs to the oil refining field, be specifically related to a kind of preparation method of super-low sulfur Hydrobon catalyst.
Background technology
The heaviness of present crude oil, in poor quality is on the rise, the output of sour crude oil (sulfur content is 0.5% ~ 2.0%) and sour crude (sulfur content is more than 2.0%) has accounted for more than 75% of world's crude oil total output in the world, wherein sulfur content surpasses 55% of world's crude oil total output at the crude oil more than 1%, the crude oil of sulfur content more than 2% also accounts for more than 30%, simultaneously, along with going from bad to worse of environment, the continuous enhancing of people's environmental consciousness, government legislation is also more and more harsher to the tail gas standard that is emitted in the atmosphere, requirement to the petroleum product-quality standard is also more and more higher, the sulfur content that namely allows is more and more lower, on January 1st, 2009, Europe came into effect Europe V " zero sulphur " diesel oil standard, and sulfur content requires below 10 μ g/g; The diesel oil sulfur content of in September, 2006 U.S.'s requirement 80% is reduced to below the l5 μ g/g from 500 μ g/g, and all carries out in 2010; Sulphur mass fraction in the Japanese diesel oil in 2005 is controlled at below the 50 μ g/g, further is reduced to below the 10 μ g/g in 2008; Also begin to carry out the clean diesel standard that sulfur content is lower than 50 μ g/g March in Beijing2008 year.In addition, the existence of nitride and affects the stability of diesel product not only bad for the carrying out of hydrodesulfurization reaction in the diesel raw material, makes the oil product color burn, and the non-oxidizability variation is therefore also very important to removing of nitride in the diesel oil in unifining process.Therefore, by improving desulfurization, the nitrogen removal performance of Hydrobon catalyst, seem very urgent with the clean diesel of production super-low sulfur for the development of petroleum refining industry.
Adopt a kind of highly active hydrogenation catalyst that has in the disclosed petroleum hydrocarbon hydrotreating method of US4880524.This catalyst is Ni-Mo/Al
2O
3Type, specific area is greater than 300m
2/ g, less than the aperture of 7nm greater than 70%.This catalyst has preferably hydrofinishing active for light ends oil, but this type of catalyst is because the limitation of its carrier and reactive metal performance can not satisfy the requirement of current deep desulfuration.
CN1040610A discloses to contain TiO
2γ-Al
2O
3Be the Hydrobon catalyst of carrier, take W-Mo-Ni as active component.With TiO
2The Al of modification
2O
3For the performance of the hydrogenation catalyst of carrier can necessarily be improved, but carrier acid amount is lower, and especially the middle strong acidity center is less, be unfavorable for the open loop fracture of azacyclo-, denitrification effect is not obvious, if the nitrogen compound content in the raw material is higher, it is active to affect the catalyst long-term operation.
CN101089130A discloses a kind of catalyst for hydrodesulfurizationfraction fraction oil, and catalyst take W, Mo, Ni, Co as active component, adds phosphate builder take aluminium oxide or silicon-containing alumina as carrier.This quaternary metallic catalyst has preferably metal dispersity, for distillate oil deep hydrogenation process good hydrodesulfurization effect is arranged, but because this catalyst uses conventional carriers and common metal dipping method, can not reduce better metal and carrier function and improve metal dispersity, limited the activity of catalyst, so its reaction condition is comparatively harsh, need under higher reaction temperature, just can reach the effect of deep desulfuration.
In the face of new clean fuel environmental regulation requirement, traditional Hydrofining Technology is faced with formidable challenges at present.All the time, hydrodesulfurization enjoys attention, but this situation changes, and the processing of high nitrogen heavy oil has become trend of the times on the one hand, and the existence of nitride suppresses the catalyst depth hydrodesulfurization performance on the other hand.The processing of the high nitrogen Crude oil from CNOOC of China has occupied suitable ratio in China petroleum refining industry, therefore need exploitation to be applicable to the catalyst of high nitrogen-containing inferior distillate oil deep hydrodesulfurizationof.Catalyst provided by the invention has the specific surface height, pore volume is large, surface acidity is moderate, the active height of metallic reducing, the advantage that the catalyst low-temperature reactivity is good, but can under lower reaction scale, produce the ultra-low-sulphur diesel that sulfur content is lower than 10 μ g/g.
Summary of the invention
The objective of the invention is on the basis of existing technology, a kind of preparation method of super-low sulfur Hydrobon catalyst is provided.
At petroleum refining field, γ-Al
2O
3Being the first-selected carrier of Hydrobon catalyst, also is present most widely used catalyst carrier.But because single alumina support is easy and active component forms stronger interaction, generates the cenotype of catalytically inactive, and only contain L acid, but when the high nitrogen petrol and diesel oil of hydrotreatment, γ-Al
2O
3L acid site and basic nitrogen strong absorption easily occurs, suppress the catalyst depth hydrodesulfurization performance.These drawbacks limit the application of single aluminium oxide in high nitrogen gasoline and diesel hydrogenation catalyst carrier inferior.
For this reason, the present invention has developed the catalyst carrier that is applicable to high nitrogen inferior distillate oil deep hydrodesulfurizationof, Al
2O
3-SiO
2-ZrO
2Multicomponent composite oxide.At macropore Al
2O
3In, introduce SiO
2The modulation carrier surface is acid, and the ratio of strong acid in suitably improving is conducive to the open loop fracture of azacyclo-, improves denitrification activity, can improve specific area and the pore volume of carrier simultaneously; Introduce ZrO
2Improve active component and carrier and interact, improve MoO
3Reducing activity, improve the low-temperature reactivity of catalyst.
Simultaneously the present invention adopts room temperature complexing method, take W-Mo-Ni-Co quaternary metal as active metal component, take P as auxiliary agent, adds metal chelating agent, has prepared the stable common maceration extract of solubility property, and adopts the saturated dipping technique of substep, supported active metal component.Described catalyst has the specific surface height, pore volume is large, surface acidity is moderate, the active height of metallic reducing, the advantage that the catalyst low-temperature reactivity is good.
The present invention is a kind of preparation method of super-low sulfur Hydrobon catalyst, it is characterized in that:
With Al
2O
3-SiO
2-ZrO
2Ternary compound oxides is carrier, at room temperature adopts the stable W-Mo-Ni-Co-P co-impregnated solution of complexing method preparation solubility property, and supported active metal component W-Mo-Ni-Co and auxiliary agent P on carrier make by the saturated dipping technique of substep;
Described Al
2O
3-SiO
2-ZrO
2Ternary oxide complex carrier preparation method process is, mediates after the macropore boehmite mixes with zirconyl nitrate and Ludox, extruded moulding, makes in lower roasting 1-8 hour in 80-150 ℃ lower dry 5-24 hour, 450～650 ℃ again;
The preparation method of described catalyst is, use the stable W-Mo-Ni-Co-P co-impregnated solution of complexometry preparation under the room temperature, then with co-impregnated solution step by step by saturated infusion process impregnated carrier, flood after 2-8 hour, again in 80-150 ℃ of dry 5-24 hour, 350～550 ℃ lower roasting 1-8 hour, make required catalyst;
Described catalyst, it is characterized in that zirconia content is 3～15wt%, silica content is 5～20wt%, nickel oxide content is 3～12 wt%, molybdenum oxide content 5～18 wt%, tungsten oxide content is 8～30wt%, and cobalt oxide content is 1～5wt%, and the auxiliary agent phosphorus pentoxide content is 1～9wt%.Pore volume ≮ the 0.25mL/g of catalyst, specific area is ≮ 160m
2/ g, mechanical strength ≮ 15N/mm.Catalyst appearance is cloverleaf pattern, bunge bedstraw herb or butterfly.
According to method for preparing catalyst of the present invention, it is characterized in that:
The compound method of W-Mo-Ni-Co-P co-impregnated solution is: tungsten compound, nickel compound, molybdenum compound, cobalt compound, phosphorus compound are mixed and add complexing agent with deionized water or ammoniacal liquor, and stirring and dissolving makes.Dipping method is for to be divided into isopyknic two parts or three parts with co-impregnated solution, by saturated infusion process impregnated carrier;
Described tungsten compound is ammonium metatungstate, nickel compound is one or more in nickel nitrate, nickel acetate and the basic nickel carbonate, molybdenum compound is one or more in molybdenum oxide, ammonium tetramolybdate and the ammonium paramolybdate, cobalt compound is one or more in cobalt nitrate, cobalt acetate and the cobalt carbonate, and phosphorus compound is phosphoric acid.Described complexing agent is one or more in ethylene glycol, diethanol amine, triethanolamine, citric acid, oxalic acid, malic acid or ethylenediamine, the aminotriacetic acid.
According to method for preparing catalyst of the present invention, it is characterized in that application purpose:
Catalyst is used for the distillate oil deep hydrodesulfurization behind reversion, feedstock oil is coking vapour, diesel fuel mixtures inferior, and wherein nitrogen content is 1500-3000ppm, and sulfur content is 2000-3000ppm; The reaction condition that catalyst is used is: reaction pressure 5～12MPa, 300～450 ℃ of reaction temperatures, volume space velocity 0.5～3.0h during liquid
-1, hydrogen to oil volume ratio 500～1000.
The technique effect that the present invention reaches:
Super-low sulfur Hydrobon catalyst provided by the invention, has the specific area height, pore volume is large, pore-size distribution is concentrated, surface acidity is moderate, active component is uniformly dispersed, the characteristics such as mechanical strength is large, be more suitable for compared with prior art, having and weakening nitrogen compound to the inhibition of catalyst activity in the hydrodesulfurization reaction of the high nitrogen petrol and diesel oil inferior that is provided by middle extra large oil, the C-S key, C-N key open loop fracture efficient is high, the reactive metal reducing activity is good, and the advantage that the catalyst low-temperature reactivity is high is compared with similar catalyst and can be produced sulfur content be lower than the following ultra-low-sulphur diesel of 10 μ g/g under lower reaction temperature.
The specific embodiment
Below will further set forth feature of the present invention by concrete example, but be not limited to example.The percentage that below relates to all is weight percentage.
Embodiment 1
By a kind of macropore aluminum hydroxide solid elastomer powder 240g, its aluminium oxide butt content is 70%, sneaks into sesbania powder 6g, 66% red fuming nitric acid (RFNA) 9g and oxalic acid 10g, add deionized water, in kneader, mediate mixing, by the banded extruder extruded moulding, obtain little of the clover of diameter 1.5mm.Drying is 12 hours in 120 ℃ of baking ovens, and roasting is 4 hours in 550 ℃ of Muffle furnaces, gets carrier Z-1, and its character sees Table 1.
In the 60mL deionized water, add 6g phosphoric acid, add and add 28g molybdenum oxide, 16g basic nickel carbonate under the thermal agitation, add again 30g ammonium metatungstate, 5g cobalt carbonate after the dissolving, stir, after it dissolves fully, be settled to 100mL and obtain the W-Mo-Ni-Co-P co-impregnated solution, place for subsequent use.
Get little of the carrier that the step makes before the 120g and add in the co-impregnated solution in dipping tank, dipping is 3 hours under the room temperature, and the bar that will wet subsequently is 120 ℃ of baking oven inner dryings 7 hours, and 450 ℃ of roastings are 4 hours in the Muffle furnace, namely get catalyst C-1, and its character sees Table 2.
Embodiment 2
By a kind of macropore aluminum hydroxide solid elastomer powder 240g, its alumina content is 70%, sneaks into 25% Ludox 88g, sesbania powder 6g, 66% red fuming nitric acid (RFNA) 9g and oxalic acid 10g, add deionized water, in kneader, mediate mixing, by the banded extruder extruded moulding, obtain little of the clover of diameter 1.5 mm.120 ℃ of baking oven inner dryings 12 hours, 550 ℃ of roastings were 4 hours in Muffle furnace, get carrier Z-2, and its character sees Table 1.
In the 120mL deionized water, add 6g phosphoric acid, add and add 28g molybdenum oxide, 16g basic nickel carbonate under the thermal agitation, add again 30g ammonium metatungstate, 5g cobalt carbonate after the dissolving, stir, after it dissolves fully, be settled to 200mL and obtain the W-Mo-Ni-Co-P co-impregnated solution, it is for subsequent use that co-impregnated solution is divided into isopyknic two parts of placements.
Get little of the carrier that the step makes before the 120g and add in a copy of it co-impregnated solution in dipping tank, dipping is 3 hours under the room temperature, and the bar that will wet subsequently is 120 ℃ of baking oven inner dryings 7 hours, and 350 ℃ of roastings are 4 hours in the Muffle furnace, and it is for subsequent use to lower the temperature.Until little be cooled to room temperature after, add in another part co-impregnated solution, at room temperature flooded 3 hours, the bar that will wet subsequently is 120 ℃ of baking oven inner dryings 7 hours, 450 ℃ of roastings are 4 hours in the Muffle furnace, namely get catalyst C-1, its character sees Table 2.
Embodiment 3
By a kind of macropore aluminum hydroxide solid elastomer powder 240g, its alumina content is 70%, sneak into 25% Ludox 88g, zirconyl nitrate 22g, sesbania powder 6g, 66% red fuming nitric acid (RFNA) 9g and polyethylene glycol (degree of polymerization 2000) 10g, add deionized water, in kneader, mediate mixing, by the banded extruder extruded moulding, obtain little of the butterfly of diameter 1.5 mm.120 ℃ of baking oven inner dryings 12 hours, 550 ℃ of roastings were 4 hours in Muffle furnace, get carrier Z-3, and its character sees Table 1.
In 120 mL deionized waters, add the 15g citric acid, add and add 28g molybdenum oxide, 16g basic nickel carbonate under the thermal agitation, add again 30g ammonium metatungstate, 5g cobalt carbonate after the dissolving, stir, after it dissolves fully, be settled to the W-Mo-Ni-Co-P co-impregnated solution that 200mL obtains complexing, it is for subsequent use that co-impregnated solution is divided into isopyknic two parts of placements.
Get little of the carrier that the step makes before the 120g and add in a copy of it co-impregnated solution in dipping tank, dipping is 3 hours under the room temperature, and the bar that will wet subsequently is 120 ℃ of baking oven inner dryings 7 hours, and 350 ℃ of roastings are 4 hours in the Muffle furnace, and it is for subsequent use to lower the temperature.Until little be cooled to room temperature after, add in another part co-impregnated solution, at room temperature flooded 3 hours, the bar that will wet subsequently is 120 ℃ of baking oven inner dryings 7 hours, 450 ℃ of roastings are 4 hours in the Muffle furnace, namely get catalyst C-2, its character sees Table 2.
Embodiment 4
The carrier preparation method is identical with carrier Z-3 in the example 3, and its character sees Table 1.
Get 60 mL concentrated ammonia liquors and add the 18g aminotriacetic acid, adding deionized water to liquor capacity after the dissolving is 120mL, stir the lower 30g of adding ammonium metatungstate, 28g molybdenum oxide, after the heating for dissolving, add again 16g basic nickel carbonate, 5g cobalt carbonate, continue to stir until fully dissolving, add at last 85% phosphoric acid solution 6g, regulator solution pH is 8, after its steady dissolution, is settled to the complexing co-impregnated solution that 200mL obtains stable alkalescence.Co-impregnated solution is divided into isopyknic two parts, places for subsequent use.
Get little of the carrier that the step makes before the 120g and add a copy of it co-impregnated solution in dipping tank, dipping is 3 hours under the room temperature, and the bar that will wet subsequently is 120 ℃ of baking oven inner dryings 7 hours, and 350 ℃ of roastings are 4 hours in the Muffle furnace, and it is for subsequent use to lower the temperature.Until little be cooled to room temperature after, add in another part co-impregnated solution, at room temperature flooded 3 hours, the bar that will wet subsequently is 120 ℃ of baking oven inner dryings 7 hours, 480 ℃ of roastings are 4 hours in the Muffle furnace, namely get catalyst C-4, its character sees Table 2.
Table 1
Table 2
Embodiment 5-8
This example illustrates that catalyst provided by the invention is for the hydrogenation reaction performance of high nitrogen inferior distillate oil.
The evaluation feedstock oil that adopts is the high nitrogen of the high-sulfur mixed fraction oil inferior that is provided by the CNOOC refinery.This feedstock oil belongs to the naphthene base crude oil of the high nitrogen of high-sulfur, is mixed by 28% coker gasoline, 70% coker gas oil, 2% coking light wax oil.
Adopt the fixed bed hydrogenation device of 50mL respectively catalyst A, B, C to be carried out hydrogenation reaction performance evaluation.
Presulfiding of catalyst condition: use to contain 3%CS
2The boat coal, with air speed 1.0h
-1, hydrogen to oil volume ratio 500:1 under the operating pressure of 8.0MPa, carries out presulfurization to catalyst.
Pre-vulcanization process is as follows:
Advance presulfurization oil under 120 ℃, behind the oil-feed 2h, constant temperature vulcanizes 2 h; Begin to heat up, be warming up to 150 ℃ with 15 ℃/h, constant temperature vulcanizes 4 h; Be warming up to 230 ℃ with 6 ℃/h, constant temperature vulcanizes 10 h; Be warming up to 290 ℃ with 6 ℃/h, constant temperature vulcanizes 6 h; Be warming up to 340 ℃ with 10 ℃/h, constant temperature vulcanizes 6 h; At last naturally be cooled to 200 ℃, presulfurization finishes.
The evaluation response condition is: operating pressure 8.0 MPa, and 340 ℃ of reaction temperatures, hydrogen to oil volume ratio 600:1, volume space velocity are 1.9 h
-1Evaluation result sees Table 3.
Comparative Examples 1-3
The explanation of this Comparative Examples is from controlling catalyst and industrial Ni-Mo/ Al
2O
3Type reference agent R-1, industrial Ni-Mo-W/ SiO
2-Al
2O
3Type reference agent R-2, industrial Ni-Mo-W-Co/ SiO
2-Al
2O
3The performance comparison of type reference agent R-3.Contrast industrial agent R-1, R-2 character see Table 2.
Adopt with example 5 same procedure and estimate the reference agent, evaluation result sees Table 3.
Table 3
Evaluation result in the table 3 can illustrate, catalyst provided by the invention when being used for the nitrogen inferior distillate oil hydrogenation reaction that extra large oil provides, at pressure 8.0 MPa, 340 ℃ of temperature, hydrogen-oil ratio is 600:1, volume space velocity is 1.5 o'clock
-1Process conditions under, have the performance of ultra-deep desulfurization.
Owing to use the saturated dipping method of substep to replace a step infusion process, and SiO
2, ZrO
2To the modification of carrier and the introducing of metal chelating agent etc., so that the catalytic activity of W-Mo-Ni-Co quaternary metallic catalyst C-1, C-2, C-3, C-4 progressively rises, and all surpassed industrial Ni-Mo/ Al Deng oxide
2O
3Type reference agent R-1, industrial Ni-Mo-W/ SiO
2-Al
2O
3Type reference agent R-2 is to the hydrodesulfurization effect of this inferior distillate oil.Data shows industrial Ni-Mo-W-Co/ SiO
2-Al
2O
3Type reference agent R-3 also can make the product sulfur content be lower than 10 μ g/g under the condition of 10 ℃ of reaction temperature raisings, but under these process conditions, its desulfurization performance then is lower than catalyst C-3 and the C-4 that this patent provides.
Claims (3)
1. the preparation method of a super-low sulfur Hydrobon catalyst is characterized in that:
With Al
2O
3-SiO
2-ZrO
2Ternary compound oxides is carrier, at room temperature adopts the stable W-Mo-Ni-Co-P co-impregnated solution of complexing method preparation solubility property, and supported active metal component W-Mo-Ni-Co and auxiliary agent P on carrier make by the saturated dipping technique of substep;
Described Al
2O
3-SiO
2-ZrO
2Ternary oxide complex carrier preparation method process is, mediates after the macropore boehmite mixes with zirconyl nitrate and Ludox, extruded moulding, makes in lower roasting 1-8 hour in 80-150 ℃ lower dry 5-24 hour, 450～650 ℃ again;
The preparation method of described catalyst is, use the stable W-Mo-Ni-Co-P co-impregnated solution of complexometry preparation under the room temperature, then with co-impregnated solution step by step by saturated infusion process impregnated carrier, flood after 2-8 hour, again in 80-150 ℃ of dry 5-24 hour, 350～550 ℃ lower roasting 1-8 hour, make required catalyst;
Described catalyst, it is characterized in that zirconia content is 3～15wt%, silica content is 5～20wt%, nickel oxide content is 3～12 wt%, molybdenum oxide content 5～18 wt%, tungsten oxide content is 8～30wt%, and cobalt oxide content is 1～5wt%, and the auxiliary agent phosphorus pentoxide content is 1～9wt%; Pore volume ≮ the 0.25mL/g of catalyst, specific area is ≮ 160m
2/ g, mechanical strength ≮ 15N/mm; Catalyst appearance is cloverleaf pattern, bunge bedstraw herb or butterfly.
2. by method for preparing catalyst claimed in claim 1, the compound method that it is characterized in that the W-Mo-Ni-Co-P co-impregnated solution is: tungsten compound, nickel compound, molybdenum compound, cobalt compound, phosphorus compound are mixed and add complexing agent with deionized water or ammoniacal liquor, and stirring and dissolving makes; Dipping method is for to be divided into isopyknic two parts or three parts with co-impregnated solution, by saturated infusion process impregnated carrier; Described tungsten compound is ammonium metatungstate, nickel compound is one or more in nickel nitrate, nickel acetate and the basic nickel carbonate, molybdenum compound is one or more in molybdenum oxide, ammonium tetramolybdate and the ammonium paramolybdate, cobalt compound is one or more in cobalt nitrate, cobalt acetate and the cobalt carbonate, and phosphorus compound is phosphoric acid; Described complexing agent is one or more in ethylene glycol, diethanol amine, triethanolamine, citric acid, oxalic acid, malic acid or ethylenediamine, the aminotriacetic acid.
3. by claim 1,2 described method for preparing catalyst, it is characterized in that application purpose: catalyst is used for the distillate oil deep hydrodesulfurization behind reversion, feedstock oil is coking vapour, diesel fuel mixtures inferior, wherein nitrogen content is 1500-3000ppm, and sulfur content is 2000-3000ppm; The reaction condition that catalyst is used is: reaction pressure 5～12MPa, 300～450 ℃ of reaction temperatures, volume space velocity 0.5～3.0h during liquid
-1, hydrogen to oil volume ratio 500～1000.
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