System and method for recovering CTA residues and purifying/regenerating catalyst

• US 7,285,677 B1
• Filed: 11/13/2006
• Issued: 10/23/2007
• Est. Priority Date: 11/13/2006
• Status: Expired due to Fees

• Current Assignee: Mechema Chemicals International Corp.
• Original Assignee: Mechema Chemicals International Corp.
• Inventors: Yen, David
• Primary Examiner(s): Eyler; Yvonne
• Assistant Examiner(s): Katakam; Sudhakar
• Application Number:
  US11/558,976
• Time in Patent Office: 344 Days
• Field of Search: 562/414, 562/412, 562/485
• US Class Current: 562/414
• CPC Class Codes: B01J 23/8892 Manganese
• CPC Class Codes: B01J 23/94 of catalysts comprising metals, oxides or hydroxides of the iron group metals or copper
• CPC Class Codes: B01J 27/128 with iron group metals or platinum group metals
• CPC Class Codes: C07C 51/47 by solid-liquid treatment; by chemisorption
• CPC Class Codes: C07C 63/26 1,4 - Benzenedicarboxylic acid
• CPC Class Codes: C22B 23/026 from spent catalysts
• CPC Class Codes: C22B 23/0453 Treatment or purification of solutions, e.g. obtained by leaching C22B23/0407 takes precedence
• CPC Class Codes: C22B 7/009 General processes for recovering metals or metallic compounds from spent catalysts for recovering specific metals C22B11/00 - C22B61/00
• CPC Class Codes: Y02P 10/20 Recycling
• CPC Class Codes: Y02P 20/584 Recycling of catalysts

Abstract

A system/method for recovering CTA (crude terephthalic acid) residues and purifying and regenerating catalyst, being used for recovering residues generated in the reaction processes of oxidation in manufacturing PTA (purified terephthalic acid) as well as purifying and regenerating the residues to form oxidized catalyst to be circulated for reusing; wherein there are mainly a CTA residue recovering system and a catalyst purifying/regenerating system. The CTA residue recovering system treats the CTA residues and collects metallic salt that is then sent to the catalyst purifying/regenerating system and is reduced by electrolyzing metal cobalt with a cobalt purifying/ regenerating system, then is passed to an oxidized catalyst producing system to produce oxidized catalyst to be circulated for use in the oxidation reaction process for manufacturing PTA.

Claims

1. A method for recovering CTA (crude terephthalic acid) residues and purifying and regenerating catalyst, being used for recovering CTA (crude terephthalic acid) residues generated in a reaction process of oxidation in manufacturing PTA (purified terephthalic acid), said system comprises following steps:

water washing CTA (crude terephthalic acid) residues;

CTA residues are added with water for stirring in order to resolve catalyst discharged from said process of oxidation of said PAT (purified terephthalic acid) into said water;

first time filtering and separating;

said catalyst resolved in water is separated from solid organic material;

sedimentation;

said catalyst resolved in said water is added with inorganic alkali being used as an agent for sedimentation to collect metallic ions in said water, and concentration of said metallic ions in said water is lowered to a level to be adapted for discharging, and metallic salt is generated;

second time filtering and separating;

said metallic salt is filtered and collected, said catalyst then is purified and regenerated to produce oxidized catalyst from said metallic salt; and

said purifying and regenerating catalyst includes steps of cobalt purifying/regenerating and oxidized catalyst producing wherein said cobalt purifying/regenerating step includes;

a) an acid solution step;

to resolve solid metal by adding inorganic acid solution;

b) a neutralization and sedimentation step;

to adjust pH value of said liquid to 4 to eliminate iron ions to form solution before extradition;

c) a resin treatment step;

to remove copper, nickel and chromium ions from said solution before extraction;

d) a metal extraction step;

to remove zinc and iron ions from said solution before extraction by extraction using organic extractant; and

e) an electrolyzing step;

to obtain metal cobalt by electrolyzing from liquid after extraction.

2. The method for recovering CTA (crude terephthalic acid) residues and purifying and regenerating catalyst as claimed in claim 1, wherein inorganic acid is added in during said step of CTA residue water washing to increase efficiency of resolution.

3. The method for recovering CTA (crude terephthalic acid) residues and purifying and regenerating catalyst as claimed in claim 1, wherein said solid organic material separated from said step of first time filtering and separating is further processed by organic material purifying and regenerating for recovering.

4. The method for recovering CTA (crude terephthalic acid) residues and purifying and regenerating catalyst as claimed in claim 2, wherein said inorganic acid added in a step of water washing said CTA residues is chosen from:

chlorhydric acid, hydrobromic acid or sulfuric acid.

5. The method for recovering CTA (crude terephthalic acid) residues and purifying and regenerating catalyst as claimed in claim 1, wherein method of filtering for said steps of first and second time filtering and separating is chosen from:

bag type filtering, plate type filtering, cross-flow filtering, centrifugation filtering, Dorr type, hydracyclone or hyperflux type filtering.

6. The method for recovering CTA (crude terephthalic acid) residues and purifying and regenerating catalyst as claimed in claim 1, wherein said organic material filtered and separated from step of first filtering and separating chosen from:

terephthalic acid, o-phtalic acid, iso-phtalic acid, benzoic acid, p-toluic acid or 4-carboxyl benzaldehyde.

7. The method for recovering CTA (crude terephthalic acid) residues and purifying and regenerating catalyst as claimed in claim 1, wherein said inorganic alkali added in said step of sedimentation is chosen from:

sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate or ammonium hydrogen carbonate.

8. The method for recovering CTA (crude terephthalic acid) residues and purifying and regenerating catalyst as claimed in claim 1, wherein water amount for said step of water washing is about 5-12 times of a gross amount of said organic material.

9. The method for recovering CTA (crude terephthalic acid) residues and purifying and regenerating catalyst as claimed in claim 1, wherein a CTA (crude terephthalic acid) residue recovering system is used to recover CTA (crude terephthalic acid) residues and to produce solid metallic salt, and a PTA (purified terephthalic acid mother liquid recovering system is used to recover PTA (purified terephthalic acid) mother liquid and to produce cobalt containing inorganic acid solution.

10. The method for recovering CTA (crude terephthalic acid) residues and purifying and regenerating catalyst as claimed in claim 9, wherein said solution step includes:

water washing;

to moisten said metallic salt to help resolution of sulfuric acid, and to help washing large amount of bromine ions or organic material;

acid solution;

to resolve metal in solid material by adding inorganic acid solution (sulfuric acid);

adding oxidant;

to oxide Fe⁺² to form Fe⁺³ for helping said neutralization step in a subsequent stage; and

first time filtering;

to separate said solid material and liquid.

11. The method for recovering CTA (crude terephthalic acid) residues and purifying and regenerating catalyst as claimed in claim 10, wherein said organic material in said water washing includes:

terephthalic acid, o-phtalic acid, iso-phtalic acid, benzoic acid, p-toluic acid, or 4-carboxyl benzaldehyde.

12. The method for recovering CTA (crude terephthalic acid) residues and purifying and regenerating catalyst as claimed in claim 10, wherein controlling condition for said acid solution is to heat up and to make temperature raised to 95°

C. and to control pH value to be below 0.3.

13. The method for recovering CTA (crude terephthalic acid) residues and purifying and regenerating catalyst as claimed in claim 10, wherein said inorganic acid added in said acid solution, in addition to sulfuric acid, includes chlorhydric acid or hydrobromic acid.

14. The method for recovering CTA (crude terephthalic acid) residues and purifying and regenerating catalyst as claimed in claim 10, wherein said oxidant added is chosen from:

potassium manganate, hydrogen peroxide, nitric acid, or introduced ozone or air.

15. The method for recovering CTA (crude terephthalic acid) residues and purifying and regenerating catalyst as claimed in claim 10, wherein said first time filtering method is chosen from:

bag type filtering, plate type filtering, cross-flow filtering, centrifugation filtering, Dorr type, hydracyclone or hyperflux type filtering.

16. The method for recovering CTA (crude terephthalic acid) residues and purifying and regenerating catalyst as claimed in claim 1, wherein said neutralization and sedimentation step includes:

neutralization;

to add OH⁻

to Fe³⁻

to get Fe(OH)₃ sediment, and

second time filtering;

to filter said Fe(OH)₃ sediment to form solution before extraction with an object of removing much iron (Fe) ions.

17. The method for recovering CTA (crude terephthalic acid) residues and purifying and regenerating catalyst as claimed in claim 16, wherein said second time filtering is chosen from:

bag type filtering, plate type filtering, cross-flow filtering, centrifugation filtering, Dorr type, hydracyclone or hyperflux type filtering.

18. The method for recovering CTA (crude terephthalic acid) residues and purifying and regenerating catalyst as claimed in claim 17, wherein pH value of said solution before extraction is increased to 2.

19. The method for recovering CTA (crude terephthalic acid) residues and purifying and regenerating catalyst as claimed in claim 1, wherein flow rate of resin in said resin treatment step for removing copper, nickel and chromium ions is 0.5 eq/litter of resin that gets 100% efficiency of adsorption.

20. The method for recovering CTA (crude terephthalic acid) residues and purifying and regenerating catalyst as claimed in claim 19, in said resin treatment step, inorganic acid is used for regeneration;

said inorganic acid is chosen from;

chlorhydric acid or hydrobromic acid or sulfuric acid.

21. The method for recovering CTA (crude terephthalic acid) residues and purifying and regenerating catalyst as claimed in claim 19, in said metal extraction step, said extractant is 2-ethylhexyl phosphate, butyl-dibutyl phosphonate or sec-octyl phenoxyl acid.

22. The method for recovering CTA (crude terephthalic acid) residues and purifying and regenerating catalyst as claimed in claim 19, in said metal extraction step, said inorganic acid is used for regeneration, is chosen from:

chlorhydric acid, hydrobromic acid or sulfuric acid.

23. The method for recovering CTA (crude terephthalic acid) residues and purifying and regenerating catalyst as claimed in claim 1, in said electrolyzing step, ammoniac salt is added to an amount of 1-10% before electrolyzing, to form complex ions for preventing sedimentation of cobalt ions (Co²⁺).

24. The method for recovering CTA (crude terephthalic acid) residues and purifying and regenerating catalyst is claimed in claim 1, wherein during electrolyzing in an electrolyzing tank, pH value is controlled within 4˜

4.2 with inorganic alkali for controlling further resolving of electrolyzed cobalt solution.

25. The method for recovering CTA (crude terephthalic acid) residues and purifying and regenerating catalyst as claimed in claim 24, in said electrolyzing step, said inorganic alkali is chosen from:

sodium hydroxide or potassium hydroxide.

26. The method for recovering CTA (crude terephthalic acid) residues and purifying and regenerating catalyst as claimed in claim 1, in said electrolyzing step, voltage for electrolyzing is 3-5 V, current is smaller than 8000 A.

27. The method for recovering CTA (crude terephthalic acid) residues and purifying and regenerating catalyst as claimed in claim 1, in said electrolyzing step, when weight percentage of cobalt in electrolyzing is reduced to be smaller than 0.2%, waste electrolyzing solution is discharged to a low cobalt content treatment area, till concentration of cobalt becomes less than 10 ppm and then said waste electrolyzing solution is discharged to a waste water treatment area.

28. The method for recovering CTA (crude terephthalic acid) residues and purifying and regenerating catalyst as claimed in claim 1, wherein metal cobalt obtained to by electrolyzing is sent into an oxidized catalyst producing system to produce oxidized catalyst to be circulated for use in said reaction process of oxidation in said manufacturing PTA (purified terephthalic acid).