PRECIOUS METAL CATALYST BRIQUETTES, PROCESS FOR THE MANUFACTURE AND FOR THE INCENERATION THEREOF

Abstract

A process for the incineration of precious metal catalyst briquettes, wherein the precious metal catalyst briquettes comprise precious metal catalyst, optionally water, and, also optionally, binder.

Claims

1. A process for the incineration of precious metal catalyst briquettes, wherein the precious metal catalyst briquettes comprise precious metal catalyst, optionally water, and, also optionally, binder.

2. The process of claim 1, wherein the precious metal catalyst briquettes comprise 60˜100 wt. % of precious metal catalyst, 0˜40 wt. % of water and 0˜20 wt. % of binder, or 50˜98 wt. % of precious metal catalyst, 2˜50 wt. % of water and 0˜20 wt. % of binder, wherein all amounts in wt. % are based on the total weight of the precious metal catalyst briquettes.

3. The process of claim 1, wherein the precious metal catalyst briquettes are in the form of honeycomb, cylinder, cone, sphere, half-sphere, prolate-spheroid, pyramid, oval and torus shape.

4. The process of claim 1, wherein the precious metal catalyst comprises at least one precious metal loaded on an at least partly combustible support.

5. The process of claim 4, wherein the at least one precious metal is selected from the group consisting of copper (Cu), gold (Au), silver (Ag), palladium (Pd), platinum (Pt), rhodium (Rh), iridium (Jr), ruthenium (Ru), osmium (Os) and Rhenium (Re).

6. The process of claim 4, wherein the at least partly combustible support is a carbonaceous-base material.

7. The process of claim 6, wherein the carbonaceous-base material is activated carbon, preferably activated carbon derived from coal, wood, fruit shell, coconut shell, walnut shell, apricot shell and/or date shell.

8. The process of claim 1, wherein the precious metal catalyst is a spent activated carbon-supported precious metal catalyst.

9. The process of claim 1, wherein the binder comprises water-dilutable or water-soluble organic material and, optionally, one or more than one additives.

10. The process of claim 9, wherein the water-dilutable or water-soluble organic material is selected from the group consisting of modified starch, cellulose, polyvinyl pyrrolidone, polyvinyl alcohols, acrylate polymers, epoxide polymers, polyvinyl acetal and mixtures thereof.

11. The process of claim 1, wherein the incineration process is performed under supply of oxidizing gas in the range of 1000-2000 NM3/hour per 500 kg of precious metal catalyst briquettes.

12. The process of claim 11, wherein the oxidizing gas is air or oxygen-enriched air with an oxygen content of up to 30 vol. %.

13. The process of claim 1, wherein the incineration process is performed at an incineration temperature in the range of 600 to 1200° C.

14. A precious metal catalyst briquette comprising at least one precious metal catalyst, optionally water, and also optionally, binder, wherein the precious metal catalyst comprises at least one precious metal loaded on an at least partly combustible support, and wherein the at least one precious metal is selected from the group consisting of copper (Cu), gold (Au), silver (Ag), palladium (Pd), platinum (Pt), rhodium (Rh), iridium (Jr), ruthenium (Ru), osmium (Os) and Rhenium (Re).

15. A process for the manufacture of the precious metal catalyst briquette of claim 14, said process comprising the steps of: (a) optionally crushing precious metal catalyst to obtain precious metal catalyst powder; (b) mixing 50˜98 wt. % of precious metal catalyst powder with 2-50 wt. % of water and, optionally, 0˜20 wt. % of binder to form a mixture, wherein all amounts in wt. % are based on the total weight of the precious metal catalyst briquette, (c) processing the mixture obtained in step (b) in a mold under a pressure of 200 KPa˜1200 KPa to obtain briquettes; (d) removing the briquettes obtained in step (c) from said mold, and, optionally, (e) partially or completely drying the briquettes so obtained to remove water.

Description

DETAILED DESCRIPTION OF THE PRESENT INVENTION

[0019] An object of the present invention is to overcome one or more of the disadvantages present in the state of the art.

[0020] A first object of the invention is to provide a process for the incineration of precious metal catalyst briquettes, in particular a process for the incineration of activated carbon-supported precious metal catalyst briquettes, and even more particular a process for the incineration of spent activated carbon-supported precious metal catalyst briquettes.

[0021] According to the process of the invention, the shape and size of the precious metal catalyst briquettes may vary. For example, the precious metal catalyst briquettes may be in the form of honeycomb, cylinder, cone, sphere, half-sphere, prolate-spheroid, pyramid, oval and torus shape, preferably honeycomb, cylinder, sphere and half-sphere, more preferably honeycomb, cylinder, and sphere. The weight of an individual precious metal catalyst briquette may lie in the range of from 100 to 1000 g, preferably in the range of from 200 to 500 g, for example 250 g.

[0022] According to the process of the invention, the incineration process may be performed in an incineration furnace.

[0023] According to the process of the invention, the incineration process may be performed under supply of oxidizing gas which may lie in the range of 1000-2000 NM3/hour (standard cubic meters per hour) per 500 kg of precious metal catalyst briquettes. The oxidizing gas may be air or oxygen-enriched air with an oxygen content of up to 30 vol. %.

[0024] According to the process of the invention, the incineration process may be performed at an incineration temperature in the range of 600 to 1200° C., preferably in the range of 650 to 900° C. The incineration process may take in the range of from 2 to 8 hours, preferably in the range of from 3 to 6 hours. The incineration process may be carried out in one step or as a multi-step process, in particular a two-step process, i.e. the incineration may be repeated one, two or more times.

[0025] The second object of the invention is to provide precious metal catalyst briquettes, in particular activated carbon-supported precious metal catalyst briquettes. The precious metal catalyst briquettes comprise precious metal catalyst and, optionally, water and, also optionally, binder.

[0026] According to the second object of the invention, in an embodiment, the precious metal catalyst briquettes may comprise 50˜98 wt. % of precious metal catalyst, 2-50 wt. % of water and, optionally, 0˜20 wt. % of binder, wherein all amounts in wt. % are based on the total weight of the precious metal catalyst briquettes. In a partially or even completely dried variant they may comprise less or even no water, i.e. they may then comprise 60˜100 wt. % of precious metal catalyst, 0-40 wt. % of water and, optionally, 0˜20 wt. % of binder, wherein all amounts in wt. % are based on the total weight of the precious metal catalyst briquettes.

[0027] According to the second object of the invention, the precious metal catalyst comprises at least one precious metal loaded on an at least partly combustible support, or, in other words, it comprises an at least partly combustible support equipped with at least one precious metal.

[0028] According to the second object of the invention, in an embodiment, the at least partly combustible support is a carbonaceous-base material, preferably activated carbon, in particular activated carbon derived from coal, wood, fruit shell, coconut shell, walnut shell, apricot shell and/or date shell.

[0029] According to the second object of the invention, in an embodiment, the precious metal catalyst is a spent activated carbon-supported precious metal catalyst.

[0030] According to one embodiment of the invention, the spent activated carbon-supported precious metal catalyst is a Pd/C catalyst, i.e. an activated carbon-supported palladium catalyst.

[0031] According to the second object of the invention, the binder comprises water-dilutable or water-soluble organic material and, optionally, one or more than one additives.

[0032] According to the second object of the invention, the water-dilutable or water-soluble organic material is selected from the group consisting of modified starch, cellulose, polyvinyl pyrrolidone, polyvinyl alcohols, acrylate polymers, epoxide polymers, polyvinyl acetal and mixtures thereof; preferably, the water-dilutable or water-soluble organic material is modified starch selected from the group consisting of hydroxyethyl starch, hydroxypropyl starch, hydroxypropenyl starch, sodium carboxymethyl starch, cross-linked sodium carboxymethyl starch, sodium starch glycolate and mixtures thereof, preferably sodium carboxymethyl starch, cross-linked sodium carboxymethyl starch and mixtures thereof.

[0033] According to the second object of the invention, the at least one additive comprises one or more mineral fillers. The mineral fillers may be selected from the group consisting of montmorillonite, hectorite, saponite, serpentine, bentonite, kaolin, sepiolite, chlorite, attapulgite, palygorskite, bauxite, borax and mixtures thereof, preferably montmorillonite, bentonite, kaolin, attapulgite, borax and mixtures thereof.

[0034] According to an embodiment, the binder may comprise 0.3 to 5 pbw (parts by weight) of sodium carboxymethyl starch, 0 to 20 pbw of bentonite and 0 to 5 pbw of borax. In another embodiment, it may comprise 0.5 to 4 pbw of sodium carboxymethyl starch, 5 to 15 pbw of bentonite and 0.5 to 3 pbw of borax.

[0035] The third object of the invention is to provide a process for the manufacture of said precious metal catalyst briquettes, and in particular, a process for the manufacture of said activated carbon-supported precious metal catalyst briquettes. The process comprises the steps of:

(a) optionally crushing precious metal catalyst to obtain precious metal catalyst powder;
(b) mixing 50˜98 wt. % of precious metal catalyst powder with 2˜50 wt. % of water and, optionally, 0˜20 wt. % of binder, wherein all amounts in wt. % are based on the total weight of the precious metal catalyst briquettes,
(c) processing the mixture obtained in step (b) in a mold under a pressure of 200 KPa˜1200 KPa to obtain briquettes;
(d) removing the briquettes obtained in step (c) from said mold, and, optionally,
(e) partially or completely drying the briquettes so obtained to remove water.

[0036] All definitions and preferences provided above for the process according to the first object of the invention and/or for the precious metal catalyst briquettes according to the second object of the invention equally apply to the process of the third object and vice versa.

[0037] Should the disclosure of any patents, patent applications, and publications, which are incorporated herein by reference conflict with the description of the present application to the extent that it may render a term unclear, the present description shall take precedence.

[0038] The invention will be described in more detail with reference to the following examples whose purpose is merely illustrative and not limitative of the scope of the invention.

EXAMPLES

Raw Materials and Devices

[0039] Spent activated carbon-supported precious metal catalyst A1, Pd/C—F catalyst commercially available from JiangShu Lianhua.
Spent activated carbon-supported precious metal catalyst A2, Pd/C catalyst commercially available form Dow-Corning and Sinopec.
Binder B1: Huahui® composite cellulose with high viscosity, commercial available from Hebei Baoding Shenghui Polymer Technology Co., Ltd.
Binder B2: mixture comprising 0.5 pbw of hydroxymethyl starch (CMS), 2.4 pbw of bentonite and 0.1 pbw of borax.
The briquette equipment (Closed-type briquette machine 120) commercially available from Henan Lantian mechanic manufacturing Company.

Preparation of Spent Activated Carbon-Supported Precious Metal Catalyst Briquette

[0040] The spent activated carbon-supported catalyst was crushed and milled in size of less than 2 mm mesh. The spent activated carbon-supported precious metal catalyst, water and binder were mixed together, according to the recipes summarized in Table 1. The mixtures so obtained were processed into honeycomb briquettes in a mold under pressure of 300 KPa by briquette equipment.

[0041] Precious metal catalyst briquette recipes are summarized in the following table:

TABLE-US-00001 TABLE 1 Precious metal catalyst briquette recipes Precious metal catalyst briquettes recipe Spent precious metal Sample catalysts (kg) Binder (kg) Water (kg) S1 A1 100 B1 6.25 25 S2 A2 100 B2 3 40

Incineration of Spent Activated Carbon-Supported Precious Metal Catalyst Briquettes and Powders

Example 1

[0042] The spent activated carbon-supported precious metal catalyst briquettes (S1) were loaded on trays in stack way. Then the trays with spent activated carbon-supported precious metal catalyst briquettes were put in a stainless steel incineration furnace for incineration at 800° C. for about 6 hours. The incineration process was performed under supply of 1500 NM3/hour of air per 500 kg precious metal catalyst briquettes. The spent activated carbon-supported precious metal catalyst briquettes burned to ashes, and then the shelf with ashes was taken out of furnace and cooled down in the air. The spent activated carbon-supported precious metal catalyst briquettes were incinerated in a stainless steel incineration furnace for two times. The ashes obtained in the 1.sup.st incineration and the 2.sup.nd incineration were collected for analysis, respectively. The loss of incineration (LOI) rate was measured according to GB 18484-2001 standard procedure.

Example 2

[0043] Incineration of spent activated carbon-supported precious metal catalyst briquettes (S1) was performed at the same condition as in example 1, except that the spent activated carbon-supported precious metal catalyst briquettes (S1) were loaded on trays in cross way.

Example 3

[0044] Incineration of spent activated carbon-supported precious metal catalyst briquettes (S2) was performed at the same condition as in example 1.

Example 4

[0045] Incineration of spent activated carbon-supported precious metal catalyst briquettes (S2) was performed at the same condition as in example 1, except that the spent activated carbon-supported precious metal catalyst briquettes (S2) were loaded on trays in cross way.

Comparative Example 1

[0046] The spent activated carbon-supported precious metal catalyst powders (A1) were loaded on trays. Then the trays with spent activated carbon-supported precious metal catalyst powders were put in a stainless steel incineration furnace for twice incineration at 800° C. for 6 hours.

Comparative Example 2

[0047] Incineration of spent activated carbon-supported precious metal catalyst powders (A2) were performed at the same condition as in comparative example 1.

[0048] The spent activated carbon-supported precious metal catalyst ash LOI rates are summarized in the following table:

TABLE-US-00002 TABLE 2 1.sup.st incineration 2.sup.nd incineration Weight Weight Weight Weight before after Ash before after Ash Loading incineration incineration Loss after LOI incineration incineration Loss after LOI EX materials briquette style (Kg) (Kg) incineration rate (Kg) (Kg) incineration rate E1 S1 yes stack 22.30 1.53 93.16% 15.81% 2.90 2.38 17.96% 0.29% E2 S1 yes cross 26.52 1.35 94.90% C1 A1 no * 18.19 2.85 84.34% 47.40% 6.29 3.30 47.57% 27.06% E3 S2 yes stack 26.72 1.78 93.32% 74.98% 4.65 2.23 51.93% 42.87% E4 S2 yes cross 30.42 2.86 90.60% C2 A2 no * 24.00 13.03 45.73% 94.35% 13.03 10.64 18.36% 90.67% * Spent activated carbon-supported precious metal catalyst powders loaded on trays evenly.

[0049] As can be seen from the ash LOI rate listed in Table 2, compared with the spent activated carbon-supported precious metal catalyst powders, the spent activated carbon-supported precious metal catalyst briquettes have low ash LOI rate, and show high combustion efficiency.