CN103769126B - A kind of preparation method of hydrotreating catalyst - Google Patents
A kind of preparation method of hydrotreating catalyst Download PDFInfo
- Publication number
- CN103769126B CN103769126B CN201210409664.4A CN201210409664A CN103769126B CN 103769126 B CN103769126 B CN 103769126B CN 201210409664 A CN201210409664 A CN 201210409664A CN 103769126 B CN103769126 B CN 103769126B
- Authority
- CN
- China
- Prior art keywords
- solution
- accordance
- active agent
- surface active
- gemini surface
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Catalysts (AREA)
Abstract
The invention discloses a kind of preparation method of hydrotreating catalyst.The method is as follows: Gemini surface active agent acid aluminium salt solution and alkali aluminate soln before flowing plastic or add Gemini surface active agent in plastic process, the alumina dry glue of gained makes alumina support, then obtains hydrotreating catalyst by infusion process supported active metals component.The inventive method is the feature utilizing Gemini surface active agent, both the advantage of cationic and anionic surfactant had been embodied, do not introduce negative and positive heteroion again simultaneously, Gemini surface active agent molecular weight is larger in addition, reaming is effective, finally can obtain larger aperture, pore volume, the hydrogenation catalyst of high strength can be kept again.Hydrotreating catalyst of the present invention is specially adapted to catalyst for hydrotreatment of residual oil.
Description
Technical field
The present invention relates to a kind of preparation method of hydrogenation catalyst, specifically for preparation method that is heavy, residual oil hydrocatalyst, the preparation method of especially HDM or hydrogenation protecting agent.
Background technology
Along with crude oil, heaviness and in poor quality and market are to the continuous increase of light-end products demand increasingly, and legislations of environmental protection increasingly stringent, residual oil weight-lightening technology just becomes one of important topic of world today's PETROLEUM PROCESSING industry.Due to containing macromolecular compounds such as a large amount of resin and asphalts in residual oil, so require that residual oil hydrocatalyst must have larger duct to ensure that these macromolecular compounds enter catalytic inner and participate in reaction.Prepare wide-aperture residual oil hydrocatalyst and depend primarily on carrier, especially adopt hydrogenation catalyst prepared by infusion process.Carrier wherein used mainly macroporous aluminium oxide, preparing macroporous aluminium oxide needs reaming just can meet the demands usually.
CN1164563A discloses a kind of method that swing method prepares alumina support.The method is that acid solution and alkaline solution alternately add in reactor, makes pH value by acid to alkaline, then by after alkali to sour alternately change 2 ~ 7 times, fully reacts 10 ~ 120 minutes, then wash 3 ~ 6 times to remove sulfate radical or sodium ion with weak aqua ammonia.The aluminium oxide aperture of this swing method gained concentrates on 4 ~ 10nm, and aperture is too little, is not suitable for the carrier being used as the large aperture catalyst such as HDM.
CN1184078A discloses a kind of preparation method of alumina support.The method adopt and flow plastic generate aluminium hydroxide as crystal seed, then pH value swing method is utilized to obtain the aluminium oxide of pore distribution concentration, wherein by changing preparation condition, the pore volume that can obtain pore diameter range 20 ~ 60nm accounts for the aluminium oxide of total pore volume more than 70%.In the alumina support of the method gained, 20 ~ 60nm is concentrated in most of hole, and the ratio shared by macropore very little, is not suitable for the carrier being used as the large aperture catalyst such as HDM.
The precursor kneading of the physics expanding agents such as the carbon black such as US4448896, US4102822, starch and activated alumina or aluminium oxide expands the aperture of alumina support, the consumption of physics expanding agent is more than aluminium oxide 10wt%, said method adds physics expanding agent in aluminium oxide precursor, and the consumption of expanding agent is large, cause the pore size distribution disperse of aluminium oxide, intensity is poor.
US4,001,144 methods disclosing the pore size distribution of a kind of modified alumina catalyst precursor, the method comprises (1) by a kind of ammonium salt aqueous solution process aluminium oxide precursor, and described ammonium salt is selected from ammonium carbonate, carbonic hydroammonium or the mixture of the two; (2) at the temperature of about 100 ~ 160 DEG C, pressurized treatments is carried out 10 ~ 24 hours with the aluminium oxide after described ammonium salt process; (3) aluminium oxide after about 100 ~ 200 DEG C of described pressurized treatments of drying about 1 ~ 24 hour, and in 500 ~ 700 DEG C of activation; (4) alumina support is reclaimed.The pore volume of the bore dia 4.5 ~ 30nm of this carrier at least accounts for 70% of cumulative volume.From properties of product, though the pore size distribution of this modified aluminas is improved, macropore ratio is still less.
CN98119912.7 discloses a kind of preparation method being suitable as the aluminium oxide of catalyst carrier for hydrgenating heavy oil, key step is contacted with a kind of precipitant solution by a kind of solution of aluminum contained compound, obtain the slurries of aluminium hydroxide, filter, wash the filter cake obtained, dry, shaping, wherein said contact, temperature 20 ~ 55 DEG C, is carried out under the condition of pH 6 ~ 9; Also have an Aging Step before filtration, describedly agingly to carry out in the medium containing carbanion and/or bicarbonate ion and ammonium ion, aging temperature 30 ~ 80 DEG C, ageing time at least 10 minutes; The method of washing is first with containing the solution washing of carbanion at least one times, then spends deionized water.The subject matter that said method exists is: (1) washing process is comparatively complicated, increases alumina producing operating cost.(2) although increase all to some extent with the aluminium oxide aperture of the method modification and pore volume, aperture is not almost had to be greater than the hole of 100nm.
CN98100800.3 discloses a kind of preparation method of the alumina support for Hydrodemetalation catalyst, key step is at the temperature of 10 ~ 300 DEG C, with containing ammonium ion and the slurry liquid contacts at least 30 minutes being selected from carbanion, the aqueous solution of bicarbonate ion and a kind of aluminium hydroxide and water, filter, and in the aluminium oxide of 500 ~ 700 DEG C of roastings.The subject matter that said method exists is as follows: it is pulled an oar with water after levigate by dried aluminium hydroxide that the aluminium hydroxide that (1) the method is used and water are pulled an oar again, or aluminum hydroxide precipitation through washing, filter after the wet cake that obtains and water pull an oar, and then with containing ammonium ion and the aqueous solution process being selected from carbanion, bicarbonate ion, process is comparatively complicated; (2) source of this patent to aluminium hydroxide used there is no special restriction, and needs reslurry, then with ammonium carbonate or ammonium bicarbonate aqueous solution process, the reaming of the aluminium carbonate salt pair aluminium oxide produced is limited.
CN101492612A discloses a kind of hydrotreating catalyst and preparation method thereof.This catalyst used carrier is with a small amount of starch and/or carbon black for crystal seed, with first and the method swung after stream prepares the slurries of aluminium hydroxide, then uses ammonium carbonate and/or carbonic hydroammonium adjust ph, finally obtains alumina support.The method can prepare the alumina support had compared with large pore volume and specific area, but preparation process is loaded down with trivial details, haves much room for improvement.
Summary of the invention
For the deficiencies in the prior art, the invention provides the preparation method of the hydrotreating catalyst that a kind of aperture is large, pore volume is large, intensity is good.The method preparation process is simple.This catalyst is used for, in residual oil demetalization course of reaction, having the ability of good desulfurization, decalcification, nickel removal, vanadium removal.
The preparation method of hydrotreating catalyst of the present invention, comprising:
(1) Gemini surface active agent solution is prepared, ie in solution A;
(2) acid aluminum salt solution is prepared, ie in solution B;
(3) alkali aluminate soln is prepared, ie in solution C;
(4) solution B, solution C stream carries out plastic reaction, pH value controls 9.0 ~ 11.0, and reaction temperature controls at 60 ~ 95 DEG C, after plastic reaction terminates, through aging, filters, washing, dry; Wherein before plastic or in plastic process, add solution A, preferred solution A and solution B, solution C are together and stream carries out plastic reaction;
(5) material of step (4) gained is through shaping, then drying and roasting obtain catalyst carrier,
(6) catalyst carrier of step (5) gained adopts infusion process load hydrogenation active metals component, then carries out drying and roasting, obtains hydrotreating catalyst.
In the inventive method, in Gemini surface active agent solution, the mass concentration of Gemini surface active agent is 0.1% ~ 5.0%.The addition of Gemini surface active agent accounts for the 0.1wt% ~ 10wt% of carrying alumina body weight.
Described Gemini surface active agent can select Bis-quaternary Ammonium Surfactants series and acetylenic glycols Gemini surface active agent 400 series in one or more.What Bis-quaternary Ammonium Surfactants series was conventional has dibrominated-N, N '-two (dimethyl dodecyl base) propane-diammonium, N, N '-dimethyl carboxybetaine, 1, two dodecyl-the N of 3-, N-dimethyl amine bromide-2-propyl alcohol, 1, two myristyl-the N of 3-, one or more in N-dimethyl amine bromide-2-propyl alcohol etc., acetylenic glycols Gemini surface active agent 400 series is conventional have in Cido-420, Cido-440, Cido-465, Cido-485 surfactant one or more.
In the inventive method, described acid aluminium salt is AlC1
3, Al
2(SO
4)
3with Al (NO
3)
3in one or more, be preferably Al
2(SO
4)
3solution; The concentration of described acid aluminium salt solution is 2 ~ 10 g A1
2o
3/ 100ml.Described basic aluminate is NaAlO
2and/or KAlO
2, the concentration of described alkali aluminate soln is 8 ~ 30g A1
2o
3/ 100ml.
The temperature of step (1), step (2), step (3) obtain solution A, solution B or solution C is 60 ~ 95 DEG C, is preferably 75 ~ 85 DEG C.
The temperature of step (4) plastic reaction is 60 ~ 95 DEG C, is preferably 75 ~ 85 DEG C.
In the inventive method, as required, add in silicate, borate and phosphate in the acid aluminium salt solution of step (2) one or more, its addition is with SiO
2, P
2o
5and/or B
2o
3meter accounts for 0.1 wt% ~ 5.0 wt% of carrying alumina body weight.Described silicate solutions is preferably sodium silicate solution, and borate solution is preferably dobell's solution, and phosphate solution is preferably ammonium phosphate solution.
Step (4) described pH value scope is 9.0 ~ 11.0, is preferably 9.5 ~ 10.5.The plastic reaction time is 30 minutes ~ 90 minutes, is preferably 40 minutes ~ 60 minutes.Described aging condition is as follows: aging temperature is 60 ~ 95 DEG C, is preferably 75 ~ 85 DEG C.Ageing time is 0.5 ~ 5 hour, preferably 1.0 ~ 3.0 hours.Described drying condition is: drying 3 ~ 10 hours at 50 ~ 140 DEG C.
Drying condition described in step (5) is: drying 3 ~ 10 hours at 50 ~ 140 DEG C; Described roasting condition is: roasting 2 ~ 10 hours at 600 ~ 800 DEG C.
Drying condition described in step (6) is be 90 ~ 130 DEG C of drying times in temperature is 1 ~ 10 hour, and roasting is be 350 ~ 550 DEG C of roastings in temperature is 1 ~ 7 hour.
In the inventive method, described hydrogenation active metals is the VIIIth race and/or group VIB metal, and wherein group VIII metal is Ni and/or Co, and group VIB metal is W and/or Mo.With the weight of catalyst for benchmark, group VIII metal with the content of oxide basis for 0.1wt% ~ 5.0wt%, group VIB metal with the content of oxide basis for 1.0wt% ~ 12.0 wt%.
Hydrotreating catalyst provided by the invention, with the weight of catalyst for benchmark, MoO
3and/or WO
3content be 1.0wt% ~ 12.0 wt%, being preferably the content of 2.0wt% ~ 10.0wt%, NiO and/or CoO is 0.5wt% ~ 5.0wt%, and be preferably 1.0wt% ~ 4.0wt%, specific area is 90 ~ 200m
2/ g, is preferably 110 ~ 160m
2/ g, pore volume is 0.60 ~ 1.40 mL/g, is preferably 0.80 ~ 1.20 mL/g.
Hydrotreating catalyst provided by the invention, most probable pore size 15 ~ 25nm, preferably 17 ~ 23nm, side pressure strength is 10 ~ 20N/mm; There is following pore size distribution: bore dia is that the pore volume in the hole being less than 10nm accounts for total pore volume 15 below %, preferably 10 below %, and the pore volume in the hole of bore dia 10 ~ 50nm accounts for 40% ~ 80% of total pore volume, preferably 46% ~ 70%; The pore volume in the hole of bore dia 100 ~ 1000nm accounts for 5% ~ 40 % of total pore volume, and preferably 5% ~ 30%.
The invention has the advantages that the hydrogenation catalyst of preparation not only has larger aperture, pore volume, can high strength be kept again.Can reduce the macromolecular compound diffusion restrictions in the catalyst such as the resin and asphalt in residual oil for residual hydrogenation reaction, the hydrogenation reaction improving catalyst is active.In the present invention, the preparation method of described macroporous aluminium oxide is the feature utilizing Gemini surface active agent, has both embodied the advantage of cationic and anionic surfactant, does not introduce Na simultaneously
+, Ca
2+, K
+, Cl
-, F
-, I
-etc. negative and positive heteroion, Gemini surface active agent molecular weight is comparatively large in addition, and reaming is effective.Finally can obtain larger aperture, pore volume, the alumina particle of high strength can be kept again, overcome in the past in alumina preparation process owing to adding a large amount of starch and/or carbon black and making the pore size distribution disperse of carrier and the poor shortcoming of intensity.
Hydrogenation catalyst of the present invention can be used as conventional hydrotreatment reaction, is specially adapted to residual hydrogenation reaction.
Detailed description of the invention
The present invention can add conventional shaping assistant as required in carrying alumina production procedure, such as peptizing agent and extrusion aid.Peptizing agent used and extrusion aid when peptizing agent wherein used and extrusion aid can adopt routine to prepare catalyst carrier for hydrgenating.Peptizing agent can be organic acid, comprises formic acid, acetic acid, citric acid, malonic acid etc.; Also can be inorganic acid, comprise nitric acid, hydrochloric acid etc.; Extrusion aid can be starch, methylcellulose, sesbania powder, formic acid, tartaric acid, citric acid; Also can be that compound helps crowded citric acid-sesbania powder etc.
Described alumina support adopts conventional shaping method to carry out, as methods such as compressing tablet, spin, extrusions.
Described baking temperature is 50 ~ 140 DEG C, preferably 80 ~ 120 DEG C; Drying time is 3 ~ 10 hours, preferably 4 ~ 8 hours, and described sintering temperature is 600 ~ 800 DEG C, is preferably 650 ~ 750 DEG C, and roasting time is be preferably 3 ~ 8 in 2 ~ 10 hours.
Described alumina support load hydrogenation active metals component adopts conventional dipping method.During preparation immersion liquid, the compound containing active metal used is soluble compound, one or more in such as molybdate, tungstates, nickel nitrate, cobalt nitrate, nickel acetate, cobalt acetate, nickelous carbonate, cobalt carbonate, nickel chloride and cobalt chloride.
According to method provided by the invention, after described impregnated activated metal, need through super-dry and roasting
Process, the condition of described drying and roasting is all conventional, such as: baking temperature is 90 ~ 130 DEG C, is preferably 100 ~ 120 DEG C; Drying time is: 1 ~ 10 hour, is preferably 2 ~ 4 hours; Sintering temperature is 350 ~ 550 DEG C, is preferably 400 ~ 500 DEG C; Roasting time is 1 ~ 7 hour, is preferably 3 ~ 6 hours;
In the present invention, catalyst specific surface and pore structure adopt the test of low temperature liquid nitrogen absorption method.Catalyst strength is the side pressure strength that the ZQJ-II Intelligent testing machine for particle adopting Dalian device diagnostic device factory to produce measures.The evaluation of catalyst carries out on 200mL fixed bed hydrogenation experimental rig.
The preparation method of catalyst of the present invention, further illustrates by following examples, but these embodiments can not limit the present invention.Wt% is mass fraction.
EXAMPLE l
By the 1L sodium metaaluminate aqueous solution (A1
2o
3concentration is 25g/100ml) and the aqueous solution (A1 of 2L aluminum sulfate
2o
3concentration is 3g/ 100ml) be respectively charged in the container of high level, lower even flowmeter flows into and 200mL water purification is housed (wherein containing 6 grams of Gemini surface active agent: N, N '-dimethyl carboxybetaine) belt stirrer and heating jacket stainless steel reactor in, the aqueous solution of the sodium metaaluminate aqueous solution and aluminum sulfate stream adds reactor carries out plastic reaction, system temperature 80 DEG C, pH value controls 9.0.React after 45 minutes and stop.Temperature to be 80 DEG C and pH value be 9.0 times aging 1.5 hours.Filter, washing.At 140 DEG C of temperature dry 3 hours, then add peptizing agent, after kneading becomes plastic, be extruded into the bunge bedstraw herb that circumscribed circle diameter is Φ 1.1 ~ 1.3, then at 140 DEG C of temperature dry 3 hours, 800 DEG C of constant temperature calcinings 4 hours, obtain catalyst carrier 1.
Take 100 grams, bunge bedstraw herb carrier, 120ml dipping solution carries out flooding (wherein MoO
3content be the content of 4.27 g/100ml, NiO be 1.33g/100ml, the content of phosphorus is 0.36g/100ml), then 110 DEG C of dryings 2 hours, 450 DEG C of roastings obtain catalyst A in 4 hours.
Embodiment 2
By the 1L sodium metaaluminate aqueous solution (A1
2o
3concentration is 20g/100ml) and the aqueous solution (A1 of 1.5L aluminum sulfate
2o
3concentration is 5g/ 100ml) be respectively charged in the container of high level, lower even flowmeter flows into and 200mL water purification is housed (wherein containing 5 grams of Gemini surface active agents: 1, two dodecyl-the N of 3-, N-dimethyl amine bromide-2-propyl alcohol) belt stirrer and heating jacket stainless steel reactor in, the aqueous solution of the sodium metaaluminate aqueous solution and aluminum sulfate stream adds reactor carries out plastic reaction, system temperature 85 DEG C, pH value controls 9.5.React after 45 minutes and stop.Temperature to be 85 DEG C and pH value be 9.0 times aging 2.0 hours.Filter, washing.At 130 DEG C of temperature dry 4 hours, then add peptizing agent, after kneading becomes plastic, be extruded into the bunge bedstraw herb that circumscribed circle diameter is Φ 1.1 ~ 1.3, then at 130 DEG C of temperature dry 4 hours, 780 DEG C of constant temperature calcinings 6 hours, obtain catalyst carrier 2.
Take 100 grams, bunge bedstraw herb carrier, 125ml dipping solution carries out flooding (wherein MoO
3content be the content of 4.18 g/100ml, NiO be 1.42g/100ml, the content of phosphorus is 0.35g/100ml), then 110 DEG C of dryings 2 hours, 450 DEG C of roastings obtain catalyst B in 4 hours.
Embodiment 3
By the 1.5L sodium metaaluminate aqueous solution (A1
2o
3concentration is 20g/100ml), the aqueous solution (A1 of 2.0L aluminum sulfate
2o
3concentration is 5g/100ml) and 200mL water purification (wherein containing 4 grams of acetylenic glycols Gemini surface active agent Cido-420), be respectively charged in the container of high level, the lower flowmeter that connects flows in the stainless steel reactor of belt stirrer and heating jacket, the aqueous solution of the sodium metaaluminate aqueous solution, aluminum sulfate and Gemini surface active agent solution stream adds reactor carries out plastic reaction, system temperature 75 DEG C, pH value controls 10.0.React after 45 minutes and stop.Temperature to be 75 DEG C and pH value be 10.0 times aging 2.0 hours.Filter, washing.At 120 DEG C of temperature dry 5 hours, then add peptizing agent, after kneading becomes plastic, be extruded into the bunge bedstraw herb that circumscribed circle diameter is Φ 1.1 ~ 1.3, then at 120 DEG C of temperature dry 5 hours, 700 DEG C of constant temperature calcinings 8.0 hours, obtain catalyst carrier 3.
Take 100 grams, bunge bedstraw herb carrier, 130ml dipping solution carries out flooding (wherein MoO
3content be the content of 3.85 g/100ml, NiO be 1.1g/100ml, the content of phosphorus is 0.33 g/100ml), then 110 DEG C of dryings 2 hours, 450 DEG C of roastings obtain catalyst C in 4 hours.
Embodiment 4
By the 1.5L sodium metaaluminate aqueous solution (A1
2o
3concentration is 20g/100ml), the aqueous solution (A1 of 2.0L aluminum sulfate
2o
3concentration is 5g/ 100ml) and 200mL water purification (wherein containing 6 gram 1, two myristyl-the N of 3-, N-dimethyl amine bromide-2-propyl alcohol Gemini surface active agent), be respectively charged in the container of high level, the lower flowmeter that connects flows in the stainless steel reactor of belt stirrer and heating jacket, the aqueous solution of the sodium metaaluminate aqueous solution, aluminum sulfate and Gemini surface active agent solution stream adds reactor carries out plastic reaction, system temperature 85 DEG C, pH value controls 10.5.React after 45 minutes and stop.Temperature to be 85 DEG C and pH value be 10.5 times aging 2.0 hours.Filter, washing.At 110 DEG C of temperature dry 5 hours, then add peptizing agent, after kneading becomes plastic, be extruded into the bunge bedstraw herb that circumscribed circle diameter is Φ 1.1 ~ 1.3, then at 110 DEG C of temperature dry 5 hours, 750 DEG C of constant temperature calcinings 7.0 hours, obtain catalyst carrier 4.
Take 100 grams, bunge bedstraw herb carrier, 118ml dipping solution carries out flooding (wherein MoO
3content be the content of 4.41 g/100ml, NiO be 1.20g/100ml, the content of phosphorus is 0.35g/100ml), then 110 DEG C of dryings 2 hours, 450 DEG C of roastings obtain catalyst D in 4 hours.
Comparative example 1
By the 1L sodium metaaluminate aqueous solution (A1
2o
3concentration is 25g/100ml) and the aqueous solution (A1 of 2L aluminum sulfate
2o
3concentration is 3g/100ml) be respectively charged in the container of high level, lower even flowmeter flows into and is equipped with in the belt stirrer of 200mL water purification and the stainless steel reactor of heating jacket, the aqueous solution of the sodium metaaluminate aqueous solution and aluminum sulfate stream adds reactor carries out plastic reaction, system temperature 80 DEG C, pH value controls 9.0.React after 45 minutes and stop.Temperature to be 80 DEG C and pH value be 9.0 times aging 1.5 hours.Filter, washing.At 140 DEG C of temperature dry 3 hours, then add peptizing agent, after kneading becomes plastic, be extruded into the bunge bedstraw herb that circumscribed circle diameter is Φ 1.1 ~ 1.3, then at 140 DEG C of temperature dry 3 hours, 800 DEG C of constant temperature calcinings 4 hours, obtain catalyst carrier 5.
Take 100 grams, bunge bedstraw herb carrier, 95ml dipping solution carries out flooding (wherein MoO
3content be the content of 5.75 g/100ml, NiO be 1.63g/100ml, the content of phosphorus is 0.48 g/100ml), then 110 DEG C of dryings 2 hours, 450 DEG C of roastings obtain catalyst E in 4 hours.
The physical property data of embodiment and comparative example 1 ~ 5 gained sample is in table 1.
The physical property of table 1 catalyst
| Catalyst is numbered | A | B | C | D | E |
| MoO 3，wt % | 4.81 | 4.73 | 5.0 | 5.2 | 5.1 |
| NiO，wt % | 1.50 | 1.61 | 1.43 | 1.42 | 1.45 |
| Specific area, m 2/g | 130 | 125 | 115 | 137 | 180 |
| Pore volume, mL/g | 0.86 | 0.88 | 0.85 | 0.83 | 0.55 |
| Most probable pore size, nm | 18 | 19 | 20 | 17 | 9 |
| Pore size distribution, % | |||||
| <10nm | 10 | 9 | 10 | 10 | 38 |
| 10~50nm | 65 | 63 | 61 | 55 | 52 |
| 100~1000nm | 15 | 18 | 20 | 24 | 2 |
| Side pressure strength, N/mm | 15 | 14 | 15 | 15 | 15 |
Table 2 feedstock oil character
| Sulphur, wt % | 1.78 |
| Calcium, μ g/g | 25.68 |
| Nickel+vanadium, μ g/g | 25.69 |
Table 3 experimental condition and result of the test
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 | |
| Operating condition | |||||
| Reaction temperature, DEG C | 285 | 285 | 285 | 285 | 285 |
| Hydrogen dividing potential drop, MPa | 8 | 8 | 8 | 8 | 8 |
| Hydrogen to oil volume ratio | 300 | 300 | 300 | 300 | 300 |
| LHSV，h -1 | 2.0 | 2.0 | 2.0 | 2.0 | 2.0 |
| Product property | |||||
| Sulphur, wt % | 0.90 | 0.95 | 0.92 | 0.92 | 1.26 |
| Calcium, μ g/g | 8.35 | 8.45 | 8.21 | 8.07 | 13.2 |
| Nickel+vanadium, μ g/g | 11.2 | 11.8 | 12.4 | 12.0 | 20.5 |
Claims (17)
1. a preparation method for hydrotreating catalyst, comprising:
(1) Gemini surface active agent solution is prepared, ie in solution A;
(2) acid aluminum salt solution is prepared, ie in solution B;
(3) alkali aluminate soln is prepared, ie in solution C;
(4) solution B, solution C stream carries out plastic reaction, pH value controls 9.0 ~ 11.0, and reaction temperature controls at 60 ~ 95 DEG C, after plastic reaction terminates, through aging, filters, washing, dry; Wherein before plastic or in plastic process, add solution A;
(5) material of step (4) gained is through shaping, then drying and roasting obtain alumina support;
(6) alumina support of step (5) gained is adopted infusion process load hydrogenation active metals component, then carry out drying and roasting, obtain hydrotreating catalyst;
Wherein, in Gemini surface active agent solution, the addition of Gemini surface active agent accounts for the 0.1wt% ~ 10wt% of carrying alumina body weight; Described Gemini surface active agent be selected from Bis-quaternary Ammonium Surfactants series and acetylenic glycols Gemini surface active agent 400 series in one or more.
2. in accordance with the method for claim 1, it is characterized in that in described Gemini surface active agent solution, the mass concentration of Gemini surface active agent is 0.1% ~ 5.0%.
3. in accordance with the method for claim 1, it is characterized in that described Bis-quaternary Ammonium Surfactants series is dibrominated-N, N '-two (dimethyl dodecyl base) propane-diammonium, N, N '-dimethyl carboxybetaine, 1, two dodecyl-the N of 3-, N-dimethyl amine bromide-2-propyl alcohol, 1, two myristyl-the N of 3-, one or more in N-dimethyl amine bromide-2-propyl alcohol, acetylenic glycols Gemini surface active agent 400 series have in Cido-420, Cido-440, Cido-465, Cido-485 surfactant one or more.
4. in accordance with the method for claim 1, it is characterized in that described solution A and solution B, solution C are together and stream carries out plastic reaction.
5. in accordance with the method for claim 1, it is characterized in that described acid aluminium salt is AlC1
3, Al
2(SO
4)
3with Al (NO
3)
3in one or more; The concentration of described acid aluminium salt solution is 2 ~ 10 g A1
2o
3/ 100ml.
6. in accordance with the method for claim 1, it is characterized in that described basic aluminate is NaAlO
2and/or KAlO
2, the concentration of described alkali aluminate soln is 8 ~ 30g A1
2o
3/ 100ml.
7. the temperature that in accordance with the method for claim 1, it is characterized in that step (1), step (2), step (3) obtain solution A, solution B or solution C is 60 ~ 95 DEG C; The temperature of step (4) plastic reaction is 60 ~ 95 DEG C.
8. the temperature that in accordance with the method for claim 1, it is characterized in that step (1), step (2), step (3) obtain solution A, solution B or solution C is 75 ~ 85 DEG C; The temperature of step (4) plastic reaction is 75 ~ 85 DEG C.
9. in accordance with the method for claim 1, it is characterized in that adding in the acid aluminium salt solution of step (2) in silicate, borate and phosphate one or more, its addition is with SiO
2, P
2o
5and/or B
2o
3meter accounts for 0.1 wt% ~ 5.0 wt% of carrying alumina body weight.
10. in accordance with the method for claim 1, it is characterized in that step (4) described pH value scope is 9.5 ~ 10.5.
11. in accordance with the method for claim 1, it is characterized in that step (4) the plastic reaction time is 30 minutes ~ 90 minutes.
12. in accordance with the method for claim 1, it is characterized in that described aging condition is as follows: aging temperature is 60 ~ 95 DEG C, and ageing time is 0.5 ~ 5 hour.
13. in accordance with the method for claim 1, it is characterized in that the drying condition described in step (4) is: drying 3 ~ 10 hours at 50 ~ 140 DEG C.
14. in accordance with the method for claim 1, is characterised in that the drying condition described in step (5) is: drying 3 ~ 10 hours at 50 ~ 140 DEG C; Described roasting condition is: roasting 2 ~ 10 hours at 600 ~ 800 DEG C.
15. in accordance with the method for claim 1, and it is characterized in that described hydrogenation active metals is the VIIIth race and/or group VIB metal, wherein group VIII metal is Ni and/or Co, and group VIB metal is W and/or Mo.
16. in accordance with the method for claim 15, it is characterized in that described hydrotreating catalyst, with the weight of catalyst for benchmark, group VIII metal with the content of oxide basis for 0.1wt% ~ 5.0wt%, group VIB metal with the content of oxide basis for 1.0wt% ~ 12.0 wt%.
17. in accordance with the method for claim 1, and the drying being characterised in that described in step (6) is be 90 ~ 130 DEG C of drying times in temperature is 1 ~ 10 hour, and roasting is 350 ~ 550 DEG C of roastings 1 ~ 7 hour in temperature.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210409664.4A CN103769126B (en) | 2012-10-24 | 2012-10-24 | A kind of preparation method of hydrotreating catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210409664.4A CN103769126B (en) | 2012-10-24 | 2012-10-24 | A kind of preparation method of hydrotreating catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103769126A CN103769126A (en) | 2014-05-07 |
| CN103769126B true CN103769126B (en) | 2015-09-30 |
Family
ID=50562160
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210409664.4A Active CN103769126B (en) | 2012-10-24 | 2012-10-24 | A kind of preparation method of hydrotreating catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103769126B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110935463B (en) * | 2018-09-25 | 2022-07-12 | 中国石油化工股份有限公司 | Preparation method of hydrodemetallization catalyst |
| CN111375418B (en) * | 2018-12-28 | 2022-09-09 | 中国石油化工股份有限公司 | Hydrogenation catalyst and preparation method thereof |
| CN111686741B (en) * | 2019-03-12 | 2023-01-10 | 中国石油化工股份有限公司 | Preparation method of copper-zinc catalyst |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101088605A (en) * | 2006-06-16 | 2007-12-19 | 中国石油化工股份有限公司 | Process of preparing alumina carrier |
| CN101088609A (en) * | 2006-06-16 | 2007-12-19 | 中国石油化工股份有限公司 | Prepn process of catalyst for residual oil hydroprocessing |
| CN101462074A (en) * | 2007-12-19 | 2009-06-24 | 中国石油化工股份有限公司 | Alumina supporter and preparation method thereof |
| CN102309959A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Preparation method for granular hydrogenation catalyst |
| EP2452924A1 (en) * | 2010-11-16 | 2012-05-16 | Italtecno S.r.l. | Plant and method for the treatment of waste liquids deriving from industrial processes |
-
2012
- 2012-10-24 CN CN201210409664.4A patent/CN103769126B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101088605A (en) * | 2006-06-16 | 2007-12-19 | 中国石油化工股份有限公司 | Process of preparing alumina carrier |
| CN101088609A (en) * | 2006-06-16 | 2007-12-19 | 中国石油化工股份有限公司 | Prepn process of catalyst for residual oil hydroprocessing |
| CN101462074A (en) * | 2007-12-19 | 2009-06-24 | 中国石油化工股份有限公司 | Alumina supporter and preparation method thereof |
| CN102309959A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Preparation method for granular hydrogenation catalyst |
| EP2452924A1 (en) * | 2010-11-16 | 2012-05-16 | Italtecno S.r.l. | Plant and method for the treatment of waste liquids deriving from industrial processes |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103769126A (en) | 2014-05-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100496719C (en) | Heavy fractional oil hydrogenation catalyst and production thereof | |
| CN102259033B (en) | Alumina carrier and preparation method thereof as well as hydrogenation catalyst and preparation method thereof | |
| CN104588024B (en) | The preparation method of hydrogenation catalyst | |
| CN103769179B (en) | A kind of preparation method of catalyst for hydrotreatment of residual oil | |
| CN101462074B (en) | Alumina supporter and preparation method thereof | |
| CN101890382B (en) | Hydrodemetallization catalyst and application thereof | |
| CN102847541B (en) | Coal tar hydrodemetalization catalyst and preparation method thereof | |
| CN100496738C (en) | Alumina supporter possessing duplicate orifice, catalyst and preparation method | |
| CN103769118B (en) | Heavy oil hydrogenation catalyst and preparation method thereof | |
| CN103769126B (en) | A kind of preparation method of hydrotreating catalyst | |
| CN104556164B (en) | A kind of macroporous aluminium oxide and preparation method thereof | |
| CN101890380B (en) | Hydrodesulfurization catalyst and application thereof | |
| CN103801346B (en) | A kind of method preparing hydrotreating catalyst | |
| CN104646009A (en) | Inferior heavy oil hydrodesulfurization catalyst and preparation method thereof | |
| CN101147866A (en) | Paraffin hydrogenation refined catalyst and its preparing process and application | |
| CN103771469B (en) | Preparation method of alumina carrier | |
| CN103801312A (en) | Preparation method for hydrotreatment catalyst | |
| CN101492612B (en) | Hydrogenation catalyst and its producing process | |
| CN104646008B (en) | A kind of inferior heavy oil hydrodesulfurization catalyst for demetalation and preparation method thereof | |
| CN103785405B (en) | A kind of Hydrodemetalation catalyst and preparation method thereof | |
| CN103769124B (en) | The preparation method of hydrotreating catalyst | |
| CN114471593B (en) | Preparation method of hydrofining catalyst | |
| CN106925286B (en) | The classification of deasphalted oil Hydrodemetalation catalyst orients preparation method | |
| CN106179383B (en) | The preparation method of hydrotreating catalyst | |
| CN104096584B (en) | A kind of residual oil hydrocatalyst and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |