CN102451722B - Preparation method of eggshell-type hydrogenation catalyst - Google Patents
Preparation method of eggshell-type hydrogenation catalyst Download PDFInfo
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Abstract
The invention discloses a preparation method of an eggshell-type hydrogenation catalyst. The preparation method is characterized in that conventional carriers are dipped in an active metal dipping solution containing one or more thickening agents and one or more active metal dispersants under the condition of air bubbling and then are subjected to drying and calcination so that the eggshell-type hydrogenation catalyst is obtained. The preparation method can effectively adjust the thickness of a surface active metal shell layer of the eggshell-type hydrogenation catalyst and the dispersity of active metals, stabilize the active metals of the eggshell-type hydrogenation catalyst, reduce the loss of the active metals, and reduce an eggshell-type hydrogenation catalyst product cost.
Description
Technical field
The present invention relates to a kind of eggshell type hydrogenization catalyst preparation method, this method can be used for preparing residuum hydrodesulfurization and denitrification catalyst, also can be used for preparing the hydrotreating catalyst of heavy distillate, also can be used for the petroleum waxes hydrofining catalytic catalyst.
Background technology
Residue fixed-bed hydrogen addition technology effectively removes impurity such as metal, sulphur, nitrogen and carbon residue in the residual oil by adding Hydrogen Energy, for catalytic cracking provides the high-quality charging.In the last few years, along with the continuous exploitation of crude oil, the heaviness of crude oil was on the rise, to the then increase day by day of demand of oil product.In order to satisfy the needs of growing oil product, must develop the catalyst that is more suitable for.
What of active metallic content the height of Catalyst Production cost depend on to a great extent.Reduce the catalyst activity tenor and be the direct approach that reduces the catalyst cost.The reactivity worth of catalyst relies on reactive metal in the activated centre that catalyst surface forms, and reduce the cost of catalyst on the basis that does not reduce the activated centre, will start with from the utilization rate of improving reactive metal.Learn that from analyze with the useless agent of crossing in the catalyst for hydrotreatment of residual oil of inactivation, the metal impurities major part is deposited on the outer surface and time outer surface of catalyst, the activated centre of catalyst center is not utilized.Therefore, the development egg-shell catalyst is a kind of effective means that improves the activated centre utilization rate.
In the preparation of general egg-shell catalyst, the selection of carrier and the carrier of conventional homogeneous catalyst are as broad as long, also some noble metal egg-shell catalyst adopts hollow carrier, the preparation method is first soaked in solvent, under the effect of capillary pressure, solvent takes the space of carrier rapidly, the active component predecessor loads on the carrier by diffusion, adsorption process gradually, because dip time is shorter, the active component predecessor that is diffused into carrier inside is just fewer, distributes so active component is eggshell in carrier.
The common method for preparing egg-shell catalyst has following several at present:
A kind of method for preparing egg-shell catalyst is quick infusion process.Detailed process document: the E.Iglesia that sees reference, S, Soled, J.Baumgartner, 5.Reyes, J.Catal.153 (1995) 108-122 and E.Peluso, C.Galarraga, H.de Lasa, Chem.Eng.Sci.56 (2001) 1239-1245.This method adopts intermittently operated, carrier is put into the glass sintering funnel that is connected with vacuum system, to contain by the fused salt of load component or solution and pour into rapidly in the funnel, and open vacuum system at dipping rapidly after 2～4 seconds unnecessary liquid is taken away, and catalyst be taken out carry out drying again.Although stir catalyst with glass bar in the preparation, but in order to obtain lamella catalyst, the time of dipping is very short, so the carrier of diverse location and the priority of maceration extract time of contact all can produce notable difference to catalyst in the funnel, cause Preparation of Catalyst inhomogeneous.And the operating time, too short making prepared repeated variation between the different batches.In addition, this method be used for large-scale production also very the difficulty.US5545674 has introduced a kind of method for preparing egg-shell catalyst: carrier is spread out on woven wire, woven wire is heated in heating furnace more than 140 ℃, take out from stove then.The solution spraying that will contain the load component is on the heat carrier on the woven wire, and by evaporate to dryness, put back in the heating furnace and reheat by the woven wire that will have catalyst again at the carrier surface of heat for the solution that contains the load component.Repeated multiple times like this is up to the enough load components of load.This method can obtain egg-shell catalyst, but because carrier transfixion on woven wire can cause catalytic active component at the shell skewness.Carrier on the woven wire must be spread out and be skim, and this just greatly reduces production efficiency.
The another kind of method for preparing egg-shell catalyst is the solution displacement method.Detailed process document: the YQ.Zhuang that sees reference, M.Claeys, E.van steen, Appl.Catal.A:General 301 (2006) 138-142.The solution displacement method is porous carrier to be immersed to take out then in a kind of water-fast liquid unnecessary liquid is drained, just in the duct, be full of liquid, carrier immersed in the aqueous solution contain the load component place certain hour, a part can be contained the aqueous solution displacement of load component in the duct near the non-water-soluble liquid of outer surface, again carrier is taken out, oven dry and roasting also can obtain egg-shell catalyst.The egg-shell catalyst shell thickness that said method obtains is very inhomogeneous, and is also very strict to the control requirement of time, and operation is more loaded down with trivial details, is not easy large-scale production.
US7087191 has introduced a kind of method for preparing egg-shell catalyst: the powder that will contain active component is made pasty state or muddy with the powder that contains refractory metal oxide with diluent, be sprayed at the surface then through handling on the inert solid particle that becomes coarse dry then, roasting.This method can guarantee that the catalyst activity component has not entered the inside of the solid particle of carrier function, but active component exists with Powdered, the active component of powder particle inside can not play a role fully, and powder sticks together by physical action and inert solid particle surface, and is many a little less than the adhesion of this physics bonding force than the chemical bond between active component and carrier surface in the catalyst of solution dipping method preparation.Therefore, to compare with the egg-shell catalyst of the formulations prepared from solutions of active component, thisly reduced the utilization ratio of active component on the one hand by the method for active component powder preparation, in addition in use under the washing away of air-flow the active component powder also be easier to come off from the inert solid particle surface.
US 5545674 has described the preparation of core/shell-type catalyst, and it is impregnated into cobalt especially cobalt nitrate solution on the bead-type substrate repeatedly by immersion or the spray method that use has middle drying or combustion step.These methods are loaded down with trivial details and time-consuming, and adopt repeatedly dipping method, and the skin that some metals can surpass the expectation penetrates in the carrier.
WO 02/07882 has described the preparation of egg-shell catalyst or its precursor, and it is by being applied to core carrier carrier surface and dry with the slurry of the particulate of solid catalyst or its precursor, the optional refractory oxide that comprises.This method has following shortcoming, and the use of catalyst or catalyst precarsor slurry is being handled and slurry evenly is applied to have difficulties aspect the core carrier.
CN 101318133A discloses a kind of lamella catalyst that is used to prepare naphtha and diesel oil, and active carbon is a carrier, and the mode of taking to spray is sprayed onto solution on the carrier of rolling, then with catalyst drying or roasting in inert gas.The bad control of catalyst shell thickness that legal system gets is flooded in weak point spraying of the present invention, and sprays bad assurance for bar shaped catalyst.
CN1736604A discloses a kind of egg shell type metal catalyst and its production and application, this catalyst is to be carrier with the hollow silicon dioxide, at least a noble metal of load and/or at least a transition metal, adopt saturated infusion process, this catalyst is mainly used in reactions such as selective hydrogenations such as alkene, alkynes and saturated hydrogenation, has good reactivity worth.The weak point of this catalyst is because the employing hollow silicon dioxide is a carrier, must cause catalyst to have lower intensity, influences the service life of catalyst.
Summary of the invention
In order to overcome weak point of the prior art, the invention provides a kind of eggshell type hydrogenization catalyst preparation method.This method can effectively be regulated the thickness of eggshell type hydrogenation catalyst surface-active metal shell, and the active metal component on the energy stable hydrogenation catalyst reduces the loss of active metal component, improves activity of such catalysts and stability.
Eggshell type hydrogenization catalyst preparation method of the present invention comprises:
(1) preparation contains the hydrogenation active metals aqueous solution of thickener, and the pH value of solution is 3.0～5.0, adds the reactive metal dispersant then, obtains dipping solution; In the dipping solution of gained, the weight concentration of reactive metal dispersant is 1.0～5.0g/100ml, and the weight concentration of thickener is 1.0～15.0g/100ml; Described reactive metal dispersant is alkylamine salt or phosphate ester salt; Described thickener is a non-ionic surface active agent;
(2) dipping solution that adds step (1) preparation in carrier floods, and bubbling air carries out bubbling in above-mentioned system, floods 1～3 hour, then 80～130 ℃ of dryings 2～14 hours in air, 350～550 ℃ of roastings 3～5 hours, obtain the eggshell type hydrogenation catalyst.
In the step (1), described reactive metal dispersant is alkylamine salt or phosphate ester salt, wherein, alkylamine salt is one or more in myristyl tributyl ammonium chloride, octadecyl trimethylammonium bromide, DTAC, dodecyl benzyl dimethyl ammonium chloride, the myristyl dimethyl Bian ammonium chloride; Phosphate ester salt is one or more in cetyl phosphate monoester, fourth octyl group phosphorodithioate, the dodecylphosphoric acid monoesters.Described thickener is a non-ionic surface active agent, be preferably in tween series non-ionic surfactants and the polyethylene glycols non-ionic surface active agent one or more, the tween series non-ionic surfactants is one or more in polysorbas20, polysorbate40, polysorbate60 and the Tween 80, and the polyethylene glycols non-ionic surface active agent is one or more in PEG400, polyethylene glycol 800, Macrogol 600 and the polyethylene glycol 1600.In the dipping solution of step (1) gained, the weight concentration of reactive metal dispersant is 1.0～5.0g/100ml, and the weight concentration of thickener is 1.0～15.0g/100ml.
In the step (1), described hydrogenation active metals is conventional hydrogenation active metals, is generally in group vib and the group VIII metal one or more.Wherein the group vib metal is preferably tungsten and/or molybdenum, and the group VIII metal is preferably nickel and/or cobalt.The process for preparation of dipping solution is as follows: the compound that will contain hydrogenation active metals joins in the deionized water, be warming up to 70～120 ℃, be incubated 0.5～3.0 hour, after treating to dissolve fully, cool the temperature to 30～60 ℃, adding thickener adjusting pH value then is 3.0～5.0, adds the reactive metal dispersant again, forms dipping solution.In the above-mentioned dipping solution, described hydrogenation active metals is preferably one or more in tungsten, molybdenum, nickel and the cobalt, the optium concentration of each reactive metal is as follows: the weight concentration of molybdenum oxide is 20～60g/100ml, the weight concentration of tungstic acid is 5～30g/100ml, the weight concentration of nickel oxide is 5～30g/100ml, and the weight concentration of cobalt oxide is 0.5～10.0g/100ml.Can also contain phosphorus in the above-mentioned dipping solution, the weight concentration of phosphorus is 0.1～5.0g/100ml, can ammonium phosphate, in the ammonium dihydrogen phosphate (ADP), phosphoric acid one or more add in maceration extracts.The described compound that contains hydrogenation active metals is specific as follows: Tungstenic compound can be in ammonium metatungstate, nitric acid tungsten, the wolframic acid one or more; Molybdate compound can be in ammonium molybdate, the nitric acid molybdenum one or more; Cobalt compound can be in cobalt oxide, cobalt nitrate, basic cobaltous carbonate, the cobalt chloride one or more; Nickel compound containing can be in nickel nitrate, nickelous sulfate, nickel chloride, basic nickel carbonate, the nickelous carbonate one or more.
The eggshell type hydrogenation catalyst of the inventive method preparation best composed as follows: the weight with catalyst is benchmark, WO
3And/or MoO
3Content be 2.0%～24.0%, be preferably 4.0%～20.0%, the content of NiO and/or CoO is 0.5%～10.0%, is preferably 1.0%～6.5%, the content of phosphorus is 1.0%～6.0%.
Carrier used among the present invention is conventional catalyst carrier for hydrgenating, is generally alumina support or contains the alumina support of auxiliary agent, and described auxiliary agent is one or more in boron, titanium, zirconium and the silicon.The preparation process of alumina support is generally as follows: aluminum hydroxide solid elastomer powder and peptizing agent are mixed pinch into after the plastic, through moulding, drying and roasting, make alumina support; Described drying condition is as follows: 80～130 ℃ of dryings 2～14 hours, roasting condition is as follows: 500～850 ℃ of roastings 4～8 hours, preferably 600～750 ℃ of roastings 4～6 hours.In the aluminium oxide preparation process, can also add expanding agent, extrusion aid, adhesive, auxiliary agent etc. as required.Described expanding agent can be physics expanding agent such as carbon black, ammonium carbonate, polyvinyl alcohol, starch etc., its consumption is counted 0.5wt%～10.0wt% with total aluminium oxide in the material, also can be chemical enlargement agent such as phosphoric acid, boric acid etc., its consumption is counted 0.5wt%～5.0wt% with total aluminium oxide in the material, also can be their mixture.Described extrusion aid is the sesbania powder, and its consumption is counted 1.0wt%～5.0wt% with total aluminium oxide in the material.Described peptizing agent is inorganic acid and/or organic acid, can be nitric acid, formic acid, acetic acid, citric acid, oxalic acid and their mixture, and its consumption is counted 0.5wt%～2.5wt% with total aluminium oxide in the material.Described adhesive is little porous aluminum oxide, and its consumption is counted 5wt%～30wt% with total aluminium oxide in the material.Described auxiliary agent is one or more in boron, titanium, zirconium and the silicon, its consumption is counted 0.5wt%～15.0wt% with total aluminium oxide in the material, above-mentioned auxiliary agent is introduced alumina support in a usual manner, introduce when becoming glue such as aluminium hydroxide, the aluminum hydroxide solid elastomer kneading process is introduced, and also can introduce by the mode of dipping.
The inventive method can be used for preparing catalyst for hydrotreatment of residual oil, can be used for preparing the hydrotreating catalyst of heavy distillate, also can be used for the petroleum waxes hydrofining catalytic catalyst.
The inventive method adds the reactive metal dispersant in the reactive metal dipping solution, can effectively control the dispersion of active component, again by adding thickener, can control the pH value of dipping solution preferably, also can control the viscosity of solution preferably, the reactive metal dipping solution of gained is highly stable, can effectively regulate the thickness of eggshell type hydrogenation catalyst surface crust and the decentralization of reactive metal, active metal component on simultaneously can also the stable hydrogenation catalyst reduces the loss of active metal component.
The catalyst that the inventive method obtains has following advantage: (1) is because the pH value of the dipping solution that is adopted is higher, can slow down the strong interaction of acid and aluminium oxide, reduced the loss of pore volume and specific surface, made final catalyst have bigger pore volume and specific area.(2) adopt the dipping solution that contains an amount of reactive metal dispersant and thickener, can make active metal component be eggshell type and be evenly distributed on catalyst surface, improved the utilization rate of active metal component in the dipping solution, reduced the catalyst cost with suitable thickness.
Further describe technical scheme of the present invention below by embodiment and comparative example, but protection scope of the present invention is not subjected to the restriction of embodiment.
Embodiment 1: the preparation of carrier
Take by weighing commercially available boehmite powder 300 grams, add 8 gram sesbania powder, carbon black 6 grams, rare nitric acid 4 grams mix the back and add proper amount of deionized water, mix under the room temperature and pinch 30 minutes, become plastic, are extruded into the bunge bedstraw herb bar shaped on banded extruder.The bar 110 ℃ of dryings 4 hours in drying box that will wet, 650 ℃ of constant temperature is 4 hours in roaster, alumina support.
Embodiment 2: Preparation of catalysts
Prepare dipping solution: ammonium molybdate, nickel nitrate and phosphoric acid are added in the entry dissolve, adding polysorbas20 adjusting pH value then is 4.0, adds myristyl tributyl ammonium chloride then and obtains dipping solution, wherein MoO
3Content be 22.1g/100ml, the content of NiO is 5.3g/100ml, the content of phosphorus is 2.1g/100ml, the content of polysorbas20 is 4.2g/100ml, the content of myristyl tributyl ammonium chloride is 1.2g/100ml.
Take by weighing dipping solution 100ml, put into dipping tank, be warming up to 40 ℃, take by weighing embodiment 1 carrier 100 grams then, put into dipping tank, feed suitable air and carry out bubbling, flood after 2 hours and to take out, 110 ℃ of dryings were 5 hours in air, 450 ℃ of roastings 4 hours, promptly get the catalyst finished product, be numbered A.
Embodiment 3: Preparation of catalysts
Method is with embodiment 2, and the pH value of dipping solution is 4.5, MoO in the dipping solution
3Content be 22.1g/100ml, the content of NiO is 5.3g/100ml, the content of phosphorus is 2.1g/100ml, the content of polysorbate40 is 5.0g/100ml, the content of octadecyl trimethylammonium bromide is 3.0g/100ml, the gained catalyst be numbered B.
Embodiment 4: Preparation of catalysts
Method is with embodiment 2, and the pH value of dipping solution is 3.5, MoO in the dipping solution
3Content be 22.1g/100ml, WO
3Content be 10.0g/100ml, the content of NiO is 5.3g/100ml, the content of phosphorus is 3.5g/100ml, the content of PEG400 is 8.1g/100ml, the content of dodecylphosphoric acid monoesters is 3.5g/100ml, the gained catalyst be numbered C.
Embodiment 5: Preparation of catalysts
Method is with embodiment 2, and the pH value of dipping solution is 4.0, MoO in the dipping solution
3Content be 22.1g/100ml, WO
3Content be 10.0g/100ml, the content of NiO is 5.3g/100ml, the content of CoO is 2.3g/100ml, the content of phosphorus is 3.0g/100ml, the content of PEG400 is 9.0g/100ml, the content of dodecyl benzyl dimethyl ammonium chloride is 3.1g/100ml.The gained catalyst be numbered D.
Comparative Examples 1: preparing carriers such as embodiment 1.
The preparation of maceration extract: ammonium molybdate, ammonium metatungstate, nickel nitrate and phosphoric acid added in the entry dissolve MoO in the dipping solution
3Content be 22.1g/100ml, WO
3Content be 10.0g/100ml, the content of NiO is 5.3g/100ml, the content of phosphorus is 4.2g/100ml, take by weighing embodiment 1 carrier 100 gram then, dipping solution 100ml sprays, then 110 ℃ of dryings 5 hours in air, 450 ℃ of roastings 4 hours, promptly get the catalyst finished product, be numbered E.
Table 1 embodiment prepares the character of catalyst
Annotate: I
W/ I
Al, I
Mo/ I
Al, I
Ni/ I
Al, I
Co/ I
AlRepresent the reactive metal atom and the aluminium atom number ratio of catalyst surface respectively.
The catalyst A that embodiment is prepared, B, C, D, E carry out the initial activity evaluation on 200ml residual hydrogenation midget plant, raw materials used oil properties sees Table 2, process conditions see Table 3 and evaluating catalyst the results are shown in Table 4.
Table 2 raw material oil properties
| S, % (mass fraction) | 3.958 |
| N, % (mass fraction) | 0.257 |
| CCR, % (mass fraction) | 12.49 |
| Ni+V，μg/g | 95.50 |
Table 3 process conditions
| Reaction temperature/℃ | 380 |
| Volume space velocity/h during liquid -1 | 0.4 |
| Reaction pressure/MPa | 15.7 |
| Hydrogen to oil volume ratio | 1000 |
Table 4 evaluating catalyst result
| The catalyst numbering | A | B | C | D | E |
| HDS/% (mass fraction) | 103 | 108 | 105 | 108 | 100 |
| HDN/% (mass fraction) | 106 | 103 | 106 | 105 | 100 |
| HDCCR/% (mass fraction) | 104 | 106 | 105 | 104 | 100 |
| HDM/% (mass fraction) | 109 | 107 | 104 | 109 | 100 |
In the table 4, HDS is the hydrodesulfurization rate, and HDN is the hydrodenitrogeneration rate, and HDCCR is the removal of ccr by hydrotreating rate, and HDM is the HDM rate.
Claims (12)
1. eggshell type hydrogenization catalyst preparation method comprises:
(1) preparation contains the hydrogenation active metals aqueous solution of thickener, and the pH value of solution is 3.0～5.0, adds the reactive metal dispersant then, obtains dipping solution; In the dipping solution of gained, the weight concentration of reactive metal dispersant is 1.0～5.0g/100mL, and the weight concentration of thickener is 1.0～15.0g/100mL; Described reactive metal dispersant is alkylammonium salt or phosphate ester salt; Described thickener is one or more in tween series and the polyethylene glycols non-ionic surface active agent;
(2) dipping solution that adds step (1) preparation in carrier floods, and bubbling air carries out bubbling in above-mentioned system, floods 1～3 hour, then 80～130 ℃ of dryings 2～14 hours in air, 350～550 ℃ of roastings 3～5 hours, obtain the eggshell type hydrogenation catalyst.
2. in accordance with the method for claim 1, it is characterized in that described alkylammonium salt is one or more in myristyl tributyl ammonium chloride, octadecyl trimethylammonium bromide, DTAC, dodecyl benzyl dimethyl ammonium chloride, the myristyl dimethyl benzyl ammonium chloride; Described phosphate ester salt is one or more in cetyl phosphate monoester, fourth octyl group phosphorodithioate, the dodecylphosphoric acid monoesters.
3. in accordance with the method for claim 1, it is characterized in that described tween series non-ionic surfactants is one or more in polysorbas20, polysorbate40, polysorbate60 and the Tween 80; The polyethylene glycols non-ionic surface active agent is one or more in PEG400, polyethylene glycol 800, Macrogol 600 and the polyethylene glycol 1600.
4. in accordance with the method for claim 1, it is characterized in that in the step (1), described hydrogenation active metals is one or more in tungsten, molybdenum, nickel and the cobalt.
5. according to claim 1 or 4 described methods, the process for preparation that it is characterized in that the described dipping solution of step (1) is as follows: the compound that will contain hydrogenation active metals joins in the deionized water, be warming up to 70～120 ℃, be incubated 0.5～3.0 hour, after treating to dissolve fully, cool the temperature to 30～60 ℃, adding thickener adjusting pH value then is 3.0～5.0, add the reactive metal dispersant again, form dipping solution.
6. in accordance with the method for claim 5, it is characterized in that the described compound that contains hydrogenation active metals is specific as follows: Tungstenic compound is one or more in ammonium metatungstate, nitric acid tungsten, the wolframic acid; Molybdate compound is one or more in ammonium molybdate, the nitric acid molybdenum; Cobalt compound is one or more in cobalt oxide, cobalt nitrate, basic cobaltous carbonate, the cobalt chloride; Nickel compound containing is one or more in nickel nitrate, nickelous sulfate, nickel chloride, basic nickel carbonate, the nickelous carbonate.
7. in accordance with the method for claim 5, it is characterized in that in the described dipping solution, the concentration of each hydrogenation active metals is as follows: the weight concentration of molybdenum oxide is 20～60g/100mL, the weight concentration of tungstic acid is 5～30g/100mL, the weight concentration of nickel oxide is 5～30g/100mL, and the weight concentration of cobalt oxide is 0.5～10.0g/100mL.
8. according to claim 1 or 7 described methods, it is characterized in that containing phosphorus in the described dipping solution, the weight concentration of phosphorus is 0.1～5.0g/100mL, in one or more adding maceration extracts in ammonium phosphate, ammonium dihydrogen phosphate (ADP), the phosphoric acid.
9. in accordance with the method for claim 8, it is characterized in that the composed as follows of described eggshell type hydrogenation catalyst: the weight with catalyst is benchmark, WO
3And/or MoO
3Content be 2.0%～24.0%, the content of NiO and/or CoO is 0.5%～10.0%, the content of phosphorus is 1.0%～6.0%.
10. in accordance with the method for claim 1, it is characterized in that used carrier is alumina support or the alumina support that contains auxiliary agent, described auxiliary agent is one or more in boron, titanium, zirconium and the silicon.
11. in accordance with the method for claim 10, it is characterized in that the preparation process of described alumina support is as follows: aluminum hydroxide solid elastomer powder and peptizing agent are mixed pinch into after the plastic,, make alumina support through moulding, drying and roasting; Described drying condition is as follows: 80～130 ℃ of dryings 2～14 hours, roasting condition was as follows: 500～850 ℃ of roastings 4～8 hours.
12. in accordance with the method for claim 11, it is characterized in that described alumina support adds one or more in expanding agent, extrusion aid, the adhesive as required in preparation process, described expanding agent comprises physics expanding agent and/or chemical enlargement agent, described extrusion aid is the sesbania powder, and described peptizing agent is inorganic acid and/or organic acid.
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| CN103769235B (en) * | 2012-10-25 | 2015-08-26 | 中国石油化工股份有限公司 | A kind of catalyst of shell distribution and application thereof |
| US20140235914A1 (en) * | 2013-02-19 | 2014-08-21 | Basf Corporation | Eggshell Catalyst Composites Containing Tungsten Oxide or Tungsten Oxide Hydrate |
| CN105833869B (en) * | 2015-01-12 | 2018-03-20 | 中国石油化工股份有限公司 | A kind of shell profile catalyst and preparation method thereof and a kind of Fischer-Tropsch synthesis method |
| WO2016122465A1 (en) | 2015-01-27 | 2016-08-04 | Celanese International Corporation | Process for producing ethanol using solid catalysts |
| US9670120B2 (en) | 2015-01-27 | 2017-06-06 | Celanese International Corporation | Process for producing ethanol using a solid catalyst |
| CN107051428B (en) * | 2017-05-31 | 2020-04-14 | 北京三聚环保新材料股份有限公司 | Preparation method of eggshell type catalyst |
| CN111822007B (en) * | 2019-04-19 | 2022-08-12 | 中国石油化工股份有限公司 | Preparation method of hydrotreating catalyst |
| CN112742424B (en) * | 2019-10-29 | 2022-11-08 | 中国石油化工股份有限公司 | Preparation method of heavy oil hydrotreating catalyst |
| CN115608371B (en) * | 2022-10-09 | 2024-04-30 | 中化泉州石化有限公司 | Eggshell type residuum hydrogenation catalyst and preparation method thereof |
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| CN101433848A (en) * | 2007-11-15 | 2009-05-20 | 中国石油化工股份有限公司 | Heavy oil hydrogenating treatment catalyst and preparation method thereof |
| CN101450313A (en) * | 2007-12-05 | 2009-06-10 | 中国石油天然气股份有限公司 | Preparation method of macropore heavy-oil hydrogenation catalyst |
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| CN101433848A (en) * | 2007-11-15 | 2009-05-20 | 中国石油化工股份有限公司 | Heavy oil hydrogenating treatment catalyst and preparation method thereof |
| CN101450313A (en) * | 2007-12-05 | 2009-06-10 | 中国石油天然气股份有限公司 | Preparation method of macropore heavy-oil hydrogenation catalyst |
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