CN103055892A - Preparation method of hydrotreating catalyst - Google Patents

Abstract

The invention provides a preparation method of a hydrotreating catalyst, comprising the following steps: uniformly mixing a carrier material and partial active component materials, kneading, forming, drying and roasting to prepare a catalyst carrier, wherein the drying temperature is 200-250 DEG C, the drying time is 1-2h, the roasting temperature is 1000-1200 DEG C, and the roasting time is 3-4h; using the aqueous solution of the remaining active components to spray and dip the catalyst carrier till saturation; taking out, dipping, drying and roasting into the catalyst, wherein the drying temperature is 150-200 DEG C, the drying time is 6-8h, the roasting temperature is 700-900 DEG C, and the roasting time is 12-24h. The finished product catalyst prepared with the method is more concentrated in pore-size distribution and relatively high in specific surface, simultaneously is beneficial to material forming, and ensures the catalyst strength and stacking density, so that corresponding service performances of the catalyst are improved.

Description

The preparation method of hydrotreating catalyst

Technical field

The present invention relates to a kind of hydrotreating catalyst and preparation method thereof.

Background technology

Usually, the hydrotreating catalyst of hydrocarbon feed is all with γ～Al ₂O ₃Or contain the γ～Al of a small amount of one or more other elements (such as Si, P, Ti, B, Mg, F etc.) ₂O ₃Be carrier, with a certain active component that is combined as of the elements such as W, Mo, Ni and Co.Such catalyst activity Metal Supported method has two kinds usually: kneading method and infusion process.Kneading method refers to and mix simultaneously active metallic compound in the carrier preparation process, and its advantage is that preparation technology is easy, and is with short production cycle, and efficient is high, and cost is low, can obtain the higher catalyst of active metallic content; Its shortcoming is that difficulty accomplishes to take full advantage of metal component.Infusion process is to make first again load active component of carrier, its advantage is to be conducive to metal component disperse at carrier micropore inner surface, but complex manufacturing, especially when single-steeping was difficult to satisfy catalyst itself to the requiring of metal addition, the complex operations of bringing by repeatedly flooding was to mention in the same breath with the easy of kneading method.For solving this class contradiction, Chinese invention patent CN1098433A has proposed a kind of solution, namely " mix-soaks " production process of combination.Its main points are to sneak into first a part of active component in the carrier preparation process, and another part active component is with the infusion process load.Owing to added metallic salt in the kneading process, for guaranteeing that shaping of catalyst is smooth and intensity good, its peptization acid amount needs corresponding raising, every 100g Al in its exemplary embodiments ₂O ₃(264g contains Al about need acetic acid 15g ₂O ₃A water alumina powder of 75% ... add 60g1: 1 acetic acid solution), thus larger to the micropore property effect of aluminium oxide, make the pore size distribution disperse of finished catalyst, the aperture is reduced to below 50% between the pore volume integration rate of 6～10nm, and specific area descends.And pore distribution concentration is greatly the precondition of good catalyst activity in certain OK range and specific area.

Summary of the invention

The invention provides a kind of preparation method of hydrotreating catalyst, the method for preparing catalyst that " mix-soaks " combination in the prior art is improved, when guaranteeing that catalyst contains higher hydrogenation active metals component, weaken acid solution to the effect of aluminium oxide.

Hydrotreating catalyst is loaded catalyst, carrier is aluminium oxide, silica and zirconia quality are than being the mixture of 1-2:1-1.5:1-2, active component is molybdenum oxide, tungsten oxide, nickel oxide, chromium oxide, ruthenium-oxide and rhodium oxide, the mass ratio of carrier and active component is that 1.5-2:1 is take the active component gross weight as benchmark, the weight content of molybdenum oxide and tungsten oxide is 35-40%, the nickel oxide weight content is 20-25%, chromium oxide, ruthenium-oxide and rhodium oxide weight content are 35-45%, the mass ratio of molybdenum oxide and tungsten oxide is 1-1.5:1-2,, chromium oxide, the mass ratio of ruthenium-oxide and rhodium oxide is 1-2:1-2:1.5-3;

Described preparation method may further comprise the steps: support material and a part of active component raw material are mixed, make catalyst carrier after the kneading, moulding, drying, roasting, baking temperature is 200-250 ° of C, be 1-2 hour drying time, sintering temperature is 1000-1200 ° of C, and roasting time is 3-4 hour; The aqueous solution with remaining active component sprays said catalyst carrier, until saturated, take out, drying and roasting is made catalyst behind the dipping, and baking temperature is 150-200 ° of C, and be 6-8 hour drying time, sintering temperature is 700-900 ° of C, and roasting time is 12-24 hour.

The catalyst granules diameter is 0.1～1mm, and the catalyst pore volume is 1.3～1.5ml/g, and average pore size is 10～25nm, and catalyst specific surface is 200～300m ²/ g.

The kneading concrete steps: adding contains Ludox and (contains SiO ₂20～50w%) acetic acid solution contains HAc 40～70w% in the solution, the acetic acid consumption is pressed 100g Al ₂O ₃Acetic acid 3～12g, kneading 3～8 hours; The gained plastic is extruded into bar shaped at banded extruder.

The objective of the invention is, so that finished catalyst has more the pore-size distribution concentrated and larger specific area, be conducive to simultaneously material forming, guarantee catalyst strength and bulk density, and then improve the corresponding serviceability such as catalyst activity.

 

The specific embodiment

Embodiment 1

(1) takes by weighing 120g aluminium oxide, 60g silica, 120g zirconia, 33.25g tungsten oxide, 47.5g nickel oxide, 15.2g chromium oxide, 15.2g ruthenium-oxide and 45.6g rhodium oxide, mix, the mixed solution that adding mixes by 178g water, with 18g acetic acid, kneading 3.5 hours, the gained plastic is extruded into the strip of Φ 0.82mm at banded extruder, drying is 1 hour under 200 ° of C, and roasting is 3 hours under 1000 ° of C.(2) take by weighing 41.5g (containing molybdenum oxide 80w%) technical grade ammonium molybdate, adding density is 0.9500g/cm ³Ammonia spirit 240cm ³Stirring and dissolving, placement is spent the night stable.(3) strip by (1) gained is placed the rotation vessel, spray into the solution by (2) preparation, until saturated, take out, drying is 6 hours under 200 ℃, again 700 ℃ of lower roastings 12 hours.

Claims (2)

1. the preparation method of a hydrotreating catalyst, it is characterized in that: described catalyst is loaded catalyst, carrier is aluminium oxide, silica and zirconia quality are than being the mixture of 1-2:1-1.5:1-2, active component is molybdenum oxide, tungsten oxide, nickel oxide, chromium oxide, ruthenium-oxide and rhodium oxide, the mass ratio of carrier and active component is that 1.5-2:1 is take the active component gross weight as benchmark, the weight content of molybdenum oxide and tungsten oxide is 35-40%, the nickel oxide weight content is 20-25%, chromium oxide, ruthenium-oxide and rhodium oxide weight content are 35-45%, the mass ratio of molybdenum oxide and tungsten oxide is 1-1.5:1-2,, chromium oxide, the mass ratio of ruthenium-oxide and rhodium oxide is 1-2:1-2:1.5-3;

Described preparation method may further comprise the steps: support material and a part of active component raw material are mixed, make catalyst carrier after the kneading, moulding, drying, roasting, baking temperature is 200-250 ° of C, be 1-2 hour drying time, sintering temperature is 1000-1200 ° of C, and roasting time is 3-4 hour; The aqueous solution with remaining active component sprays said catalyst carrier, until saturated, take out, drying and roasting is made catalyst behind the dipping, and baking temperature is 150-200 ° of C, and be 6-8 hour drying time, sintering temperature is 700-900 ° of C, and roasting time is 12-24 hour.

2. preparation method according to claim 1, the catalyst granules diameter is 0.1～1mm, and the catalyst pore volume is 1.3～1.5ml/g, and average pore size is 10～25nm, and catalyst specific surface is 200～300m ²/ g.