Pseudo-boehmite, manufacturing process and application thereof

Patent metadata

Field	Value
Publication number	US-12421128-B2
Application number	US-201917309878-A
Country	US
Kind code	B2
Filing date	Dec 27, 2019
Priority date	Dec 28, 2018
Publication date	Sep 23, 2025
Grant date	Sep 23, 2025

Abstract

A pseudo-boehmite has a dry basis content of 55-85 wt % and contains a phosphoric acid ester group. The sodium oxide content is not greater than 0.5 wt %, and the phosphorus content (in terms of phosphorus pentoxide) is 1.2-5.7 wt %, relative to 100 wt % of the total weight of the pseudo-boehmite. The pseudo-boehmite has a low sodium content.

First claim

The invention claimed is:

1. A manufacturing process of pseudo-boehmite, comprising:
contacting an alkaline aluminium source, a cation-exchange resin, and an organic acid source in the presence of water to obtain a mixed liquid, wherein the organic acid source is selected from at least one of mono-C 9 -C 15 -alkylether phosphoric acid ester, mono-C 9 -C 15 -alkylphosphoric acid ester, di-C 9 -C 15 -alkylphosphoric acid ester, and di-C 9 -C 15 -alkylether phosphoric acid ester; and
separating the mixed liquid to obtain the pseudo-boehmite, wherein a weight ratio of the alkaline aluminium source, calculated based on alumina, to the organic acid source is 1.2:1 to 24:1,
wherein the contacting step comprises:
S1: reacting the alkaline aluminum source, the organic acid source, and a first portion of the cation-exchange resin in the presence of water in a reactor to obtain a first mixture having a pH value of 7.5-10; and
S2: aging the first mixture, and then adding thereto a second portion of the cation-exchange resin to obtain the mixed liquid having a pH value of 6.5-7.5, and
wherein the separating step comprises:
S3: separating the cation-exchange resin from the mixed liquid to obtain a slurry;
S4: separating the slurry to obtain a filtrate and a filter cake; and
S5: drying the filter cake to obtain the pseudo-boehmite,
wherein the filter cake is not washed, and the pseudo-boehmite contains a dry content of 55-85 wt %, no more than 0.5 wt % of sodium oxide, 1.2-5.7 wt % of the organic acid source, calculated based on phosphorous pentoxide, relative to 100 wt % of a total weight of the pseudo-boehmite,
wherein the alkaline aluminium source is selected from aluminate, metaaluminate, and sodium metaaluminate,
wherein the organic acid source is of formula (I),

wherein each A is identical to or different from each other, each independently selected from hydrogen ion, ammonium ion (NH 4 + ), metal ion, and a group of formula

 R0 is an optionally substituted C9-15 linear or branched alkyl, n groups R 1 are, identical to or different from each other, each independently selected from C1-6 linear or branched alkylene, n is a number in the range of 0 to 200,
wherein the cation-exchange resin is an acidic cation-exchange resin, a weight ratio of the first portion and the second portion of the cation-exchange resin is 4:1 to 8:1,
in S1, the reaction temperature is 45° C.-80° C.,
in S2, the aging temperature is 50-100° C., the ageing time is 0.5-3 hours, and
an amount of water is 5-20 vol % of the total volume of the reactor.

2. The manufacturing process of claim 1 , wherein the weight ratio of the alkaline aluminium source, calculated based on alumina, to the organic acid source is 5:1 to 20:1, and/or, a particle size of the cation-exchange resin is 20-150 mesh.

3. The manufacturing process of claim 1 , wherein:
in S1, the alkaline aluminium source is in an aqueous solution having a concentration, calculated based on Al 2 O 3 , of 20-100 g Al 2 O 3 /L, the organic acid source is in an aqueous solution having a concentration of 0.05-0.5 g/mL, and the cation-exchange resin is in a suspension having a solid content of 30-80 wt %.

4. The manufacturing process of claim 3 , wherein: in S1,
the amount of water is 5-15 vol % of the total volume of the reactor,
the aqueous solution of the alkaline aluminium source is added to the reactor at a flow rate of 30 mL/min-50 mL/min,
the amount of the suspension of the cation-exchange resin added to the reactor maintains the pH value of the first mixture at 8.0-9.5.

5. The manufacturing process of claim 3 , wherein in S2, the amount of the suspension of the cation-exchange resin added to the reactor maintains the pH value of the mixed liquid at 6.5-7.0.

6. The manufacturing process of claim 1 , wherein:
the alkaline aluminium source is an aluminate,
the organic acid source has an acidity coefficient pKa of 2-8 or a HLB (Hydrophilic Lipophilic Balance) value of 3-8.

7. The manufacturing process of claim 6 , wherein:
the alkaline aluminium source is sodium meta-aluminate,
and the organic acid source has an acidity coefficient pKa of 3-6 or a HLB value of 3-6.

8. The manufacturing process of claim 1 , wherein:
at least one A is hydrogen ion,
R0 is C9-15 linear or branched alkyl,
n groups R1 are, identical to or different from each other, each independently selected from C2-4 linear or branched alkylene, and
n is a number in the range of 0 to 100.

9. The manufacturing process of claim 8 , wherein both of two As are hydrogen ion, R0 is C9 linear or branched alkyl, n groups R1 are each ethylene, and n is a number in the range of 5 to 20.

10. The manufacturing process of claim 1 , wherein in S1, the reaction temperature is 50° C.-75° C. and the pH value of the first mixture is 8.0-9.5.

11. A manufacturing process of alumina, consisting of the following steps:
manufacturing the pseudo-boehmite according to the manufacturing process of claim 1 ; and
calcining the pseudo-boehmite to obtain an alumina,
wherein the alumina has a phosphorus content, calculated based on the phosphorus element, of 0.3-5.0 wt %, a pore volume of 0.7-1.2 mL/g, a unit surface acid amount of 0.001-0.002 mmol/m 2 , and a hydraulicity of 3-10 N/particle.

12. A manufacturing process of a hydrogenation catalyst, consisting of the following steps:
manufacturing all the pseudo-boehmite according to the manufacturing process of claim 1 ;
shaping, drying and calcining the pseudo-boehmite to obtain a support; and
loading a catalytic active component selected from at least one of Mo, W, Ni, and Co on said support to obtain the catalyst.

Assignees

• China Petroleum & Chem Corp
• Dalian Res Institute Of Petroleum And Petrochemicals Sinopec Corp

Inventors

• Zhu Huihong
• Yang Tao
• Liu Tiebin
• Jin Hao
• Yang Guang
• Liu Lu
• Lv Zhenhui
• Fang Xiangchen

Classifications

• B01J35/40

  characterised by dimensions, e.g. grain size (in a colloidal state B01J35/23; crystallite size B01J35/77) · CPC title

• C10G49/04

  containing nickel, cobalt, chromium, molybdenum, or tungsten metals, or compounds thereof · CPC title

• C01F7/46

  Purification of aluminium oxide, aluminium hydroxide or aluminates (C01F7/028 takes precedence) · CPC title

• C01F7/441

  by calcination · CPC title

• B01J21/04 Primary

  Alumina · CPC title