CN109402403B - Method for trapping platinum group metals in spent catalyst by pickling sludge - Google Patents

Abstract

The invention discloses a method for trapping platinum group metals in a spent catalyst by pickling sludge, belonging to the field of regenerated platinum group metals. The acid-washing sludge is smelted after being pretreated and mixed with the spent catalyst and the slag former, and platinum group metals in the spent catalyst are comprehensively recovered. The invention uses the acid-washing sludge as the platinum group metal trapping agent after pretreatment, thereby not only having high economic benefit, reducing the pollution to the environment, realizing the harmless disposal and high-value utilization of secondary resources, but also being capable of efficiently recovering the platinum group metal in the ineffective catalyst.

Description

Method for trapping platinum group metals in spent catalyst by pickling sludge

Technical Field

The invention belongs to the technical field of regenerated platinum group, and particularly relates to a method for trapping platinum group metals in a spent catalyst by acid-washing sludge.

Background

Platinum group metals have the characteristics of high melting point, high boiling point, low steam pressure, good oxidation resistance and corrosion resistance, high catalytic activity and the like, are widely applied to catalysts, high-temperature corrosion alloys and the like, and the consumption of the platinum group metals is increased year by year. However, since the abundance of platinum group metals is extremely low and the distribution of mineral resources is extremely unbalanced, the world proportion of platinum group metal resources in our country is only 2.14%, and therefore, it is imperative to recover platinum group metals from secondary resources containing platinum group metals.

The spent catalyst is an important secondary resource containing platinum group metals (mainly platinum, rhodium, palladium). The recovery of platinum group metals from spent catalysts is a critical step in achieving effective separation of the platinum group metals from the support. The current platinum group metal recovery methods are mainly wet and pyrogenic.

The wet method is mainly oxidation leaching of an acid medium, can be divided into a full dissolution method, an active component dissolution method and a carrier dissolution method, has simple process and low factory building cost, is generally adopted by small and medium-sized recovery enterprises, but has generally low leaching rate of wet recovery of platinum group metals. The pyrogenic process includes a metal trapping method, a plasma melting method, a chlorination volatilization method, and the like. The metal trapping method is widely applied, and platinum group metal trapping agents mainly comprise metal lead, copper oxide and the like, and are seriously polluted due to toxic metal.

The Chinese invention patent (application number 200910094317.5) discloses a method for extracting platinum group metals from a spent catalyst by a wet-fire combination method, which comprises the steps of crushing the spent automobile exhaust catalyst, adding hydrochloric acid and an oxidant to leach the platinum group metals, adding iron powder and zinc powder to replace the platinum group metals to obtain platinum group metal powder, uniformly mixing leached residues with a trapping agent and a slag former, and smelting to enable the platinum group metals to enter a metal phase. The method has the characteristic of high recovery rate of the platinum group metals, but the use of iron powder and zinc powder for replacing the platinum group metals has high material consumption and energy consumption, long flow path and serious heavy metal pollution. The Chinese invention patent (application number 201210060308.6) discloses a method for extracting platinum group metals from a spent automobile exhaust catalyst by a smelting enrichment-wet separation process, wherein the spent automobile exhaust catalyst is uniformly mixed with auxiliary materials such as iron ore concentrate and the like, and then the platinum group metals are enriched in an alloy by smelting; carrying out acidolysis to separate base metals and obtain platinum group metal powder after alloy pulverization, and finally smelting to obtain the platinum group metal. The method has the advantages of high recovery rate of platinum group metal, short process and low cost. The patent adopts iron ore concentrate as a trapping agent, platinum group metals are enriched by a pyrogenic process, and then platinum group metal powder is obtained by acidolysis, so that the problems of large acid-containing wastewater amount, serious secondary pollution and the like exist. The Chinese invention patent (application No. 201510235965.3) discloses a method for recovering platinum group metals based on copper capture, which comprises the steps of mixing and agglomerating a spent petroleum catalyst, a spent automobile catalyst, a copper capture agent (copper sulfate and copper oxide), a reducing agent (coal and coke), an additive (lime, quartz sand and borax) and a binder, then carrying out reduction roasting, and crushing, ball milling and gravity separation on the reduced metallized pellets to obtain copper alloy powder containing the platinum group metals. The patent has high recovery rate of platinum group metals and simple process, but the ball milling process is adopted to crush the pellets and reselect and separate nonmetal and metal phases in the pellets, so that the production amount of waste water is large, the energy consumption is high, and the pollution of heavy metal copper ions is serious. The Chinese invention patent (application number 201611141140.6) discloses a method for extracting noble metal by taking an iron-based material as a trapping agent, which is used for trapping noble metal and then carrying out electrolysis or acidolysis, but the method adopts high-temperature reduction roasting, needs to add a reducing agent and needs to protect atmosphere, and has high limitation. The invention patent of china (application No. 201410189468.X) discloses a method for preparing a regenerated ferroalloy from acid-washed sludge of a sewage treatment plant, wherein the acid-washed sludge, quicklime and anthracite are mixed and stirred, the pH value is adjusted to be neutral, and the regenerated ferroalloy is obtained after sintering in a rotary kiln and smelting in a plasma furnace. The invention patent (application No. 201580032856.X) discloses a method for recovering platinum group metals from spent catalysts by subjecting chlorine gas to an electromagnetic field to promote chlorine ionization and formation of volatile chlorides with the platinum group metals in the spent catalysts at a predetermined temperature, and finally cooling to obtain a solid phase material containing platinum group metals. The method has novel idea and wide application range, but the process needs a chlorination reactor and an electromagnetic inductor, the equipment requirement is higher, the industrial production difficulty is high, and the chlorine and the chloride aqueous solution generated in the reaction process have serious pollution to the environment. The invention patent (application No. 201080020551.4) discloses a method for recovering precious metals from spent homogeneous catalysts by using pyrometallurgical processes to destroy organic waste in the catalyst and enrich the platinum group metals with matte. Because the matte contains heavy metals such as copper, lead and arsenic, the heavy metal pollution is serious.

Therefore, the existing process for recovering platinum group metals from the spent catalyst has the problems of high material consumption and energy consumption, large wastewater yield, serious secondary pollution and the like, so that the research and development of a method for efficiently recovering platinum group metals from the spent catalyst in a green way are urgently needed.

Disclosure of Invention

In order to solve the technical problems, the invention provides a method for collecting platinum group metals in a spent catalyst by acid washing sludge. The method utilizes the acid-washing sludge as the platinum group metal trapping agent, not only effectively recovers the platinum group metals, but also reduces the reaction cost, reduces the environmental pollution and realizes the efficient green recovery of the platinum group metals.

The invention is realized by the following technical scheme:

a method for collecting platinum group metals in a spent catalyst by acid-washing sludge comprises the steps of dehydrating and deoiling the acid-washing sludge to obtain iron alloy powder, mixing the iron alloy powder serving as a platinum group metal collecting agent with the spent catalyst and a slagging agent, and smelting to form a platinum group metal-rich iron alloy.

Further, the conditions for dehydrating and deoiling the acid-washed sludge are controlled as follows: the dehydration temperature is 100-120 ℃, and the dehydration time is 10-120 min; the deoiling temperature is 180-320 ℃, and the deoiling time is 10-120 min.

Further, the mass ratio of the ferroalloy powder to the spent catalyst to the slagging agent is controlled as follows: 5-20 wt% of ferroalloy powder, 50-70 wt% of spent catalyst and 20-35 wt% of slagging agent, wherein the total weight of the ferroalloy powder, the spent catalyst and the slagging agent is 100 wt%.

Further, crushing the spent catalyst, and mixing the crushed spent catalyst with the ferroalloy powder and the slag former, wherein the particle size of the crushed spent catalyst is 0.1-20 mm;

the failure catalyst is one or more of failure automobile catalyst, failure petroleum catalyst and failure chemical catalyst.

Further, the slagging agent comprises CaO and Na₂CO₃、CaF₂One or more of borax and borax;

in the mixture of the ferroalloy powder, the spent catalyst and the slag former, the addition amount of each component of the slag former is respectively CaO 15-30 wt% and Na₂CO₃ 0～20wt％、CaF₂0-5 wt% of borax and 0-5 wt%.

Further, smelting a mixture of the ferroalloy powder, the spent catalyst and the slag former at 1300-1600 ℃ for 30-180 min, and separating a slag phase from an iron phase to obtain a platinum group metal-rich ferroalloy and waste slag; the platinum group metal trapping rate is 90.0-99.7%, and the platinum group metal grade of the waste slag is less than or equal to 5 g/t.

The invention has the beneficial technical effects that:

1) compared with the traditional method for preparing the platinum group metal trapping agent by using heavy metals (such as lead and copper) as the platinum group metal trapping agent, the method disclosed by the invention has the advantages that the platinum group metal trapping agent is prepared by using the acid-washed sludge as the raw material, the trapping rate of the platinum group metal is high, the harmless utilization of dangerous solid wastes is realized, the toxic heavy metal trapping agent is avoided, the heavy metal pollution is avoided, and the method has the advantages of high recovery rate of the platinum group metal, simple process, no pollution, low cost, wide applicability and easiness in industrial production.

2) According to the method, the iron alloy is prepared by dehydrating and deoiling the acid-washed sludge, so that low-energy-consumption recovery is realized, and the prepared iron alloy can efficiently trap platinum group metals;

3) according to the method, the acid-washing sludge is used as the raw material to prepare the platinum group metal trapping agent, so that the high-value utilization and cooperative disposal of the ineffective catalyst in the harmless disposal of the acid-washing sludge are realized, the 'best use of the material' is realized, and the raw material cost is reduced;

4) borax, calcium fluoride and slag phases in the slagging agent adopted by the method form eutectic phases, so that the melting point of the slag phases is reduced, and further the melting temperature and energy consumption are reduced;

5) the method has the advantages of high platinum group metal trapping rate (more than 90 percent) and low platinum group metal content (less than or equal to 5g/t) in the waste slag;

6) the method is suitable for recovering various catalysts containing platinum group metals, such as invalid automobile catalysts, invalid petroleum catalysts and invalid chemical catalysts, and has the advantages of simple process, wide application range and easy industrial production.

Drawings

FIG. 1 is a schematic flow chart of a method for capturing platinum group metals in a spent catalyst by acid washing sludge in an embodiment of the invention.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

On the contrary, the invention is intended to cover alternatives, modifications, equivalents and alternatives which may be included within the spirit and scope of the invention as defined by the appended claims. Furthermore, in the following detailed description of the present invention, certain specific details are set forth in order to provide a better understanding of the present invention. It will be apparent to one skilled in the art that the present invention may be practiced without these specific details.

Example 1

And (3) dehydrating the acid-washed sludge at 120 ℃ for 40min, and then deoiling at 250 ℃ for 60min to obtain the ferroalloy powder. 20 wt% of iron alloyUniformly mixing gold powder, 50 wt% of failed automobile catalyst crushed aggregates and 30 wt% of slagging agent to obtain a mixture, wherein the slagging agent is prepared from 25 wt% of CaO and 2 wt% of Na₂CO₃2 wt% of CaF₂And 1 wt% of borax. Heating the mixture to 1450 ℃, smelting for 60min, and separating a slag phase from an iron phase to obtain a platinum group metal-rich iron alloy and waste slag, wherein the platinum group metal trapping rate is 98.8%, and the platinum group metal in the slag phase is 2.8g/t in grade.

Example 2

Dehydrating the acid-washed sludge at 119 ℃ for 10min, and deoiling at 180 ℃ for 120min to obtain the ferroalloy powder. And uniformly mixing 20 wt% of ferroalloy powder, 50 wt% of failed petroleum catalyst crushed aggregates and 30 wt% of slagging agent to obtain a mixture, wherein the slagging agent consists of 30 wt% of CaO. Heating the mixture to 1300 ℃ to smelt for 180min, separating a slag phase from an iron phase to obtain the platinum group metal-rich iron alloy and waste slag, wherein the platinum group metal trapping rate is 90%, and the platinum group metal in the slag phase is 5g/t in grade.

Example 3

And dehydrating the acid-washed sludge at 118 ℃ for 15min, and deoiling at 200 ℃ for 115min to obtain the ferroalloy powder. Uniformly mixing 15 wt% of ferroalloy powder, 65 wt% of failed chemical catalyst crushed aggregates and 20 wt% of slagging agent to obtain a mixture, wherein the slagging agent is prepared from 17 wt% of CaO and 3 wt% of Na₂CO₃And (4) forming. Heating the mixture to 1350 ℃, smelting for 170min, and separating a slag phase from an iron phase to obtain the platinum group metal-rich iron alloy and waste slag, wherein the platinum group metal trapping rate is 90.8%, and the platinum group metal in the slag phase is 4.8 g/t.

Example 4

And dehydrating the acid-washed sludge at 117 ℃ for 25min, and deoiling at 210 ℃ for 95min to obtain the ferroalloy powder. Uniformly mixing 10 wt% of ferroalloy powder, 35 wt% of failed automobile catalyst crushed aggregates, 35 wt% of failed petroleum catalyst crushed aggregates and 20 wt% of slagging agent to obtain a mixture, wherein the slagging agent is prepared from 16 wt% of CaO and 4 wt% of CaF₂And (4) forming. Heating the mixture to 1400 ℃, smelting for 150min, and separating a slag phase from an iron phase to obtain a platinum group metal-rich iron alloy and waste slag, wherein the platinum group metal trapping rate is 93.5%, and the platinum group metal in the slag phase is 3.7g/t in grade.

Example 5

And (3) dehydrating the acid-washed sludge at 110 ℃ for 35min, and then deoiling at 250 ℃ for 80min to obtain the ferroalloy powder. Uniformly mixing 5 wt% of ferroalloy powder, 30 wt% of failed automobile catalyst crushed aggregates, 35 wt% of failed chemical catalyst crushed aggregates and 30 wt% of slag former to obtain a mixture, wherein the slag former consists of 25 wt% of CaO and 5 wt% of borax. Heating the mixture to 1430 ℃ for smelting for 120min, and separating a slag phase from an iron phase to obtain a platinum group metal-rich iron alloy and waste slag, wherein the platinum group metal trapping rate is 92.1%, and the platinum group metal in the slag phase is 3.9g/t in grade.

Example 6

And (3) dehydrating the acid-washed sludge at 116 ℃ for 20min, and then deoiling at 260 ℃ for 75min to obtain the ferroalloy powder. Uniformly mixing 7 wt% of ferroalloy powder, 33 wt% of failed petroleum catalyst crushed aggregates, 35 wt% of failed chemical catalyst crushed aggregates and 25 wt% of slagging agent to obtain a mixture, wherein the slagging agent is prepared from 18 wt% of CaO and 4 wt% of Na₂CO₃And 3 wt% of CaF₂And (4) forming. Heating the mixture to 1480 ℃ for smelting for 110min, and separating a slag phase from an iron phase to obtain a platinum group metal-rich iron alloy and waste slag, wherein the platinum group metal trapping rate is 92.8%, and the grade of the platinum group metal in the slag phase is 3.5 g/t.

Example 7

And dehydrating the acid-washed sludge at 105 ℃ for 55min, and deoiling at 190 ℃ for 105min to obtain the ferroalloy powder. Uniformly mixing 6 wt% of ferroalloy powder, 20 wt% of failed automobile catalyst crushed aggregates, 20 wt% of failed petroleum catalyst crushed aggregates, 29 wt% of failed chemical catalyst crushed aggregates and 25 wt% of slagging agent to obtain a mixture, wherein the slagging agent is prepared from 15 wt% of CaO, 6 wt% of Na₂CO₃And 4 wt% of borax. Heating the mixture to 1550 ℃ for smelting for 80min, and separating a slag phase from an iron phase to obtain a platinum group metal-rich iron alloy and waste slag, wherein the platinum group metal trapping rate is 92.3%, and the grade of platinum group metal in the slag phase is 3.8 g/t.

Example 8

And (3) dehydrating the acid-washed sludge at 114 ℃ for 80min, and then deoiling at 320 ℃ for 30min to obtain the ferroalloy powder. 10 wt% ferroalloy fines with 20 wt% spent automotive catalyst chaff, 20 wt% spent petroleum catalyst chaff, 20 wt% spentUniformly mixing the industrial catalyst crushed aggregates and 30 wt% of a slagging agent to obtain a mixture, wherein the slagging agent is prepared from 19 wt% of CaO and 8 wt% of Na₂CO₃And 3 wt% of CaF₂And (4) forming. Heating the mixture to 1530 ℃ to smelt for 55min, separating a slag phase from an iron phase to obtain the iron alloy rich in the platinum group metal and waste slag, wherein the platinum group metal trapping rate is 96.3%, and the platinum group metal in the slag phase is 3.1g/t in grade.

Example 9

And (3) dehydrating the acid-washed sludge at 113 ℃ for 100min, and then deoiling at 220 ℃ for 100min to obtain the ferroalloy powder. Uniformly mixing 20 wt% of ferroalloy powder, 20 wt% of failed automobile catalyst crushed aggregates, 20 wt% of failed petroleum catalyst crushed aggregates, 20 wt% of failed chemical catalyst crushed aggregates and 20 wt% of slagging agent to obtain a mixture, wherein the slagging agent is prepared from 15 wt% of CaO, 2 wt% of CaF₂And 3 wt% of borax. Heating the mixture to 1600 ℃ for smelting for 30min, and separating a slag phase from an iron phase to obtain the iron alloy rich in platinum group metals and waste slag, wherein the platinum group metal trapping rate is 97.6%, and the platinum group metals in the slag phase are 3g/t in grade.

Example 10

And (3) dehydrating the acid-washed sludge at 100 ℃ for 120min, and then deoiling at 300 ℃ for 20min to obtain the ferroalloy powder. Uniformly mixing 20 wt% of ferroalloy powder, 30 wt% of failed automobile catalyst crushed aggregates, 10 wt% of failed petroleum catalyst crushed aggregates, 10 wt% of failed chemical catalyst crushed aggregates and 30 wt% of slagging agent to obtain a mixture, wherein the slagging agent is prepared from 21 wt% of CaO, 5 wt% of Na₂CO₃1 wt% of CaF₂And 3 wt% of borax. Heating the mixture to 1520 ℃ to smelt for 90min, separating a slag phase from an iron phase to obtain the iron alloy rich in platinum group metals and waste slag, wherein the platinum group metal trapping rate is 98.3%, and the platinum group metals in the slag phase are 2.9g/t in grade.

Example 11

And dehydrating the acid-washed sludge at 115 ℃ for 65min, and deoiling at 295 ℃ for 55min to obtain the ferroalloy powder. Uniformly mixing 20 wt% of ferroalloy powder, 30 wt% of failed automobile catalyst crushed aggregates, 10 wt% of failed petroleum catalyst crushed aggregates, 10 wt% of failed chemical catalyst crushed aggregates and 30 wt% of slagging agent to obtain a mixture, wherein the slagging agent is prepared from 15 wt% of CaO, 11 wt% of Na₂CO₃1 wt% of CaF₂And 3 wt% of borax. Heating the mixture to 1540 ℃, smelting for 120min, and separating a slag phase and an iron phase to obtain the iron alloy rich in platinum group metals and waste slag, wherein the platinum group metal trapping rate is 98.8%, and the grade of the platinum group metals in the slag phase is 2.8 g/t.

Example 12

And (3) dehydrating the acid-washed sludge at 109 ℃ for 75min, and then deoiling at 270 ℃ for 90min to obtain the ferroalloy powder. Mixing 18 wt% of ferroalloy powder, 20 wt% of failed automobile catalyst crushed aggregates, 25 wt% of failed petroleum catalyst crushed aggregates, 5 wt% of failed chemical catalyst crushed aggregates and 32 wt% of slagging agent uniformly to obtain a mixture, wherein the slagging agent is prepared from 15 wt% of CaO, 12 wt% of Na₂CO₃2 wt% of CaF₂And 3 wt% of borax. Heating the mixture to 1590 ℃ for smelting for 45min, separating a slag phase and an iron phase to obtain a platinum group metal-rich iron alloy and waste slag, wherein the platinum group metal trapping rate is 98.9%, and the platinum group metal in the slag phase is 2.8g/t in grade.

Example 13

And (3) dehydrating the acid-washed sludge at 101 ℃ for 70min, and then deoiling at 240 ℃ for 110min to obtain the ferroalloy powder. Uniformly mixing 17 wt% of ferroalloy powder, 5 wt% of failed automobile catalyst crushed aggregates, 25 wt% of failed petroleum catalyst crushed aggregates, 20 wt% of failed chemical catalyst crushed aggregates and 33 wt% of slagging agent to obtain a mixture, wherein the slagging agent is prepared from 15 wt% of CaO, 13 wt% of Na₂CO₃3 wt% of CaF₂And 2 wt% of borax. Heating the mixture to 1450 ℃ for smelting for 85min, and separating a slag phase from an iron phase to obtain the iron alloy rich in platinum group metals and waste slag, wherein the platinum group metal trapping rate is 99.1 percent, and the platinum group metals in the slag phase have a grade of 2.7 g/t.

Example 14

And (3) dehydrating the pickling sludge at 111 ℃ for 50min, and then deoiling at 290 ℃ for 25min to obtain the ferroalloy powder. Uniformly mixing 14 wt% of ferroalloy powder, 11 wt% of failed automobile catalyst crushed aggregates, 30 wt% of failed petroleum catalyst crushed aggregates, 10 wt% of failed chemical catalyst crushed aggregates and 35 wt% of slagging agent to obtain a mixture, wherein the slagging agent is prepared from 15 wt% of CaO, 17 wt% of Na₂CO₃And 3 wt% of borax. And heating the mixture to 1550 ℃ for smelting for 30min, and separating a slag phase from an iron phase to obtain a platinum group metal-rich iron alloy and waste slag, wherein the platinum group metal trapping rate is 99.7%, and the grade of platinum group metal in the slag phase is 2.6 g/t.

Example 15

And (3) dehydrating the acid-washed sludge at 112 ℃ for 60min, and then deoiling at 310 ℃ for 15min to obtain the ferroalloy powder. Uniformly mixing 10 wt% of ferroalloy powder, 23 wt% of failed automobile catalyst crushed aggregates, 30 wt% of failed petroleum catalyst crushed aggregates, 10 wt% of failed chemical catalyst crushed aggregates and 27 wt% of slagging agent to obtain a mixture, wherein the slagging agent is prepared from 22 wt% of CaO, 1 wt% of Na₂CO₃2 wt% of CaF₂And 2 wt% of borax. Heating the mixture to 1580 ℃ for smelting for 50min, and separating a slag phase from an iron phase to obtain a platinum group metal-rich iron alloy and waste slag, wherein the platinum group metal trapping rate is 99.5%, and the platinum group metal in the slag phase is 2.7g/t in grade.

Example 16

And (3) dehydrating the acid-washed sludge at 108 ℃ for 90min, and then deoiling at 290 ℃ for 40min to obtain the ferroalloy powder. Uniformly mixing 12 wt% of ferroalloy powder, 30 wt% of failed automobile catalyst crushed aggregates, 10 wt% of failed petroleum catalyst crushed aggregates, 13 wt% of failed chemical catalyst crushed aggregates and 35 wt% of slagging agent to obtain a mixture, wherein the slagging agent is prepared from 26 wt% of CaO and 9 wt% of Na₂CO₃And (4) forming. Heating the mixture to 1490 ℃ for smelting for 60min, and separating a slag phase from an iron phase to obtain a platinum group metal-rich iron alloy and waste slag, wherein the platinum group metal trapping rate is 99.6%, and the platinum group metal in the slag phase is 2.8g/t in grade.

Example 17

And (3) dehydrating the acid-washed sludge at 105 ℃ for 120min, and then deoiling at 300 ℃ for 50min to obtain the ferroalloy powder. Uniformly mixing 11 wt% of ferroalloy powder, 30 wt% of failed automobile catalyst crushed aggregates, 10 wt% of failed petroleum catalyst crushed aggregates, 14 wt% of failed chemical catalyst crushed aggregates and 35 wt% of slagging agent to obtain a mixture, wherein the slagging agent is prepared from 24 wt% of CaO, 7 wt% of Na₂CO₃1 wt% of CaF₂And 3 wt% of borax. Heating the mixture to 1560 deg.C, smelting for 70min, and separating slag phase and iron phase to obtain iron rich in platinum group metalAlloy and waste slag, the platinum group metal trapping rate is 99.7 percent, and the platinum group metal grade in the slag phase is 2.4 g/t.

Example 18

And dehydrating the acid-washed sludge at 115 ℃ for 30min, and deoiling at 285 ℃ for 65min to obtain the iron alloy powder. Uniformly mixing 13 wt% of ferroalloy powder, 30 wt% of failed automobile catalyst crushed aggregates, 12 wt% of failed petroleum catalyst crushed aggregates, 10 wt% of failed chemical catalyst crushed aggregates and 35 wt% of slagging agent to obtain a mixture, wherein the slagging agent is prepared from 25 wt% of CaO, 5 wt% of Na₂CO₃2 wt% of CaF₂And 3 wt% of borax. Heating the mixture to 1580 ℃ for smelting for 80min, and separating a slag phase from an iron phase to obtain a platinum group metal-rich iron alloy and waste slag, wherein the platinum group metal trapping rate is 99.7%, and the platinum group metal in the slag phase is 2.5g/t in grade.

Example 19

And dehydrating the acid-washed sludge at 103 ℃ for 115min, and deoiling at 305 ℃ for 45min to obtain the ferroalloy powder. Uniformly mixing 15 wt% of ferroalloy powder, 25 wt% of failed automobile catalyst crushed aggregates, 10 wt% of failed petroleum catalyst crushed aggregates, 15 wt% of failed chemical catalyst crushed aggregates and 35 wt% of slagging agent to obtain a mixture, wherein the slagging agent is prepared from 28 wt% of CaO, 5 wt% of Na₂CO₃And 2 wt% of CaF₂And (4) forming. Heating the mixture to 1450 ℃, smelting for 60min, and separating a slag phase from an iron phase to obtain the iron alloy rich in platinum group metals and waste slag, wherein the platinum group metal trapping rate is 99.6%, and the platinum group metals in the slag phase have a grade of 2.8 g/t.

Example 20

And (3) dehydrating the acid-washed sludge at 120 ℃ for 10min, and then deoiling at 310 ℃ for 20min to obtain the ferroalloy powder. Uniformly mixing 20 wt% of ferroalloy powder, 25 wt% of failed automobile catalyst crushed aggregates, 15 wt% of failed petroleum catalyst crushed aggregates, 10 wt% of failed chemical catalyst crushed aggregates and 30 wt% of slagging agent to obtain a mixture, wherein the slagging agent is prepared from 20 wt% of CaO, 2 wt% of Na₂CO₃5 wt% of CaF₂And 3 wt% of borax. Heating the mixture to 1470 ℃, smelting for 95min, separating a slag phase and an iron phase to obtain a platinum group metal-rich iron alloy and waste slag, wherein the platinum group metal trapping rate is 99%, and the platinum group metal in the slag phaseThe grade is 3 g/t.

Example 21

And (3) dehydrating the acid-washed sludge at 102 ℃ for 95min, and then deoiling at 305 ℃ for 70min to obtain the ferroalloy powder. Uniformly mixing 16 wt% of ferroalloy powder, 25 wt% of failed automobile catalyst crushed aggregates, 15 wt% of failed petroleum catalyst crushed aggregates, 10 wt% of failed chemical catalyst crushed aggregates and 34 wt% of slagging agent to obtain a mixture, wherein the slagging agent is prepared from 27 wt% of CaO, 1 wt% of Na₂CO₃2 wt% of CaF₂And 4 wt% of borax. Heating the mixture to 1510 ℃ to smelt for 65min, separating a slag phase from an iron phase to obtain a platinum group metal-rich iron alloy and waste slag, wherein the platinum group metal trapping rate is 99.1%, and the platinum group metal in the slag phase is 3.1g/t in grade.

Example 22

And (3) dehydrating the acid-washed sludge at 104 ℃ for 85min, and then deoiling at 315 ℃ for 35min to obtain the ferroalloy powder. Uniformly mixing 19 wt% of ferroalloy powder, 25 wt% of failed automobile catalyst crushed aggregates, 15 wt% of failed petroleum catalyst crushed aggregates, 11 wt% of failed chemical catalyst crushed aggregates and 30 wt% of slagging agent to obtain a mixture, wherein the slagging agent is prepared from 23 wt% of CaO, 2 wt% of Na₂CO₃And 5 wt% of CaF₂And (4) forming. And heating the mixture to 1440 ℃, smelting for 85min, and separating a slag phase from an iron phase to obtain a platinum group metal-rich iron alloy and waste slag, wherein the platinum group metal trapping rate is 99.3%, and the platinum group metal in the slag phase is 2.8g/t in grade.

Example 23

Dehydrating the acid-washed sludge at 115 ℃ for 45min, and deoiling at 315 ℃ for 10min to obtain the ferroalloy powder. Uniformly mixing 8 wt% of ferroalloy powder, 10 wt% of failed automobile catalyst crushed aggregates, 17 wt% of failed petroleum catalyst crushed aggregates, 30 wt% of failed chemical catalyst crushed aggregates and 35 wt% of slagging agent to obtain a mixture, wherein the slagging agent is prepared from 15 wt% of CaO, 10 wt% of Na₂CO₃5 wt% of CaF₂And 5 wt% of borax. Heating the mixture to 1500 ℃ to smelt for 75min, separating a slag phase from an iron phase to obtain the iron alloy rich in platinum group metals and waste slag, wherein the platinum group metal trapping rate is 98.5%, and the platinum group metals in the slag phase are 3.2g/t in grade.

Example 24

And dehydrating the acid-washed sludge at 107 ℃ for 105min, and deoiling at 280 ℃ for 65min to obtain the ferroalloy powder. Uniformly mixing 9 wt% of ferroalloy powder, 16 wt% of failed automobile catalyst crushed aggregates, 10 wt% of failed petroleum catalyst crushed aggregates, 30 wt% of failed chemical catalyst crushed aggregates and 35 wt% of slagging agent to obtain a mixture, wherein the slagging agent is prepared from 15 wt% of CaO, 15 wt% of Na₂CO₃And 5 wt% of borax. Heating the mixture to 1600 ℃ for smelting for 35min, and separating a slag phase from an iron phase to obtain the iron alloy rich in platinum group metals and waste slag, wherein the platinum group metal trapping rate is 99.3%, and the platinum group metals in the slag phase have a grade of 2.9 g/t.

Example 25

And (3) dehydrating the acid-washed sludge at 106 ℃ for 110min, and then deoiling at 230 ℃ for 85min to obtain the ferroalloy powder. Uniformly mixing 15 wt% of ferroalloy powder, 10 wt% of failed automobile catalyst crushed aggregates, 30 wt% of failed petroleum catalyst crushed aggregates, 10 wt% of failed chemical catalyst crushed aggregates and 35 wt% of slagging agent to obtain a mixture, wherein the slagging agent is prepared from 15 wt% of CaO, 18 wt% of Na₂CO₃2 wt% of CaF₂And (4) forming. Heating the mixture to 1570 ℃ for smelting for 40min, and separating a slag phase from an iron phase to obtain a platinum group metal-rich iron alloy and waste slag, wherein the platinum group metal trapping rate is 99.3%, and the platinum group metal in the slag phase is 3g/t in grade.

Example 26

And (3) dehydrating the acid-washed sludge at 111 ℃ for 80min, and deoiling at 305 ℃ for 26min to obtain the ferroalloy powder. Uniformly mixing 5 wt% of ferroalloy powder, 15 wt% of failed automobile catalyst crushed aggregates, 5 wt% of failed petroleum catalyst crushed aggregates, 40 wt% of failed chemical catalyst crushed aggregates and 35 wt% of slagging agent to obtain a mixture, wherein the slagging agent is prepared from 15 wt% of CaO and 20 wt% of Na₂CO₃And (4) forming. Heating the mixture to 1330 ℃ for smelting for 100min, and separating a slag phase from an iron phase to obtain the iron alloy rich in platinum group metals and waste slag, wherein the platinum group metal trapping rate is 99.4 percent, and the grade of the platinum group metals in the slag phase is 2.9 g/t.

Example 27

And dehydrating the acid-washed sludge at 116 ℃ for 66min, and deoiling at 275 ℃ for 85min to obtain the ferroalloy powder. 19 wt% of ferroalloy powder and 13 wt%The waste automobile catalyst crushed aggregates, 27 wt% of waste petroleum catalyst crushed aggregates, 10 wt% of waste chemical catalyst crushed aggregates and 31 wt% of slagging agent are mixed evenly to obtain a mixture, wherein the slagging agent is prepared by 29 wt% of CaO and 2 wt% of Na₂CO₃And (4) forming. Heating the mixture to 1370 ℃, smelting for 160min, and separating a slag phase from an iron phase to obtain a platinum group metal-rich iron alloy and waste slag, wherein the platinum group metal trapping rate is 98.8%, and the grade of the platinum group metal in the slag phase is 3.1 g/t.

Example 28

And dehydrating the acid-washed sludge at 117 ℃ for 60min, and deoiling at 288 ℃ for 97min to obtain the ferroalloy powder. Uniformly mixing 16 wt% of ferroalloy powder, 24 wt% of failed automobile catalyst crushed aggregates, 10 wt% of failed petroleum catalyst crushed aggregates, 18 wt% of failed chemical catalyst crushed aggregates and 32 wt% of slagging agent to obtain a mixture, wherein the slagging agent is prepared by mixing 16 wt% of CaO and 16 wt% of Na₂CO₃And (4) forming. Heating the mixture to 1560 ℃, smelting for 140min, and separating a slag phase from an iron phase to obtain a platinum group metal-rich iron alloy and waste slag, wherein the platinum group metal trapping rate is 99.1%, and the platinum group metal in the slag phase is 3.2g/t in grade.

Example 29

And dehydrating the acid-washed sludge at 117 ℃ for 60min, and deoiling at 288 ℃ for 97min to obtain the ferroalloy powder. 8 wt% of ferroalloy powder, 17 wt% of failed automobile catalyst crushed aggregates, 23 wt% of failed petroleum catalyst crushed aggregates, 20 wt% of failed chemical catalyst crushed aggregates and 32 wt% of slagging agent are mixed uniformly to obtain a mixture, wherein the slagging agent is prepared by 17 wt% of CaO, 14 wt% of Na₂CO₃And 1 wt% borax. Heating the mixture to 1530 ℃ to smelt for 130min, separating a slag phase from an iron phase to obtain the iron alloy rich in the platinum group metal and waste slag, wherein the platinum group metal trapping rate is 98.5%, and the platinum group metal in the slag phase is 3.6g/t in grade.

Claims (3)

1. A method for collecting platinum group metals in a spent catalyst by pickling sludge is characterized in that the pickling sludge is dehydrated and deoiled to obtain iron alloy powder, and the iron alloy powder is used as a platinum group metal collecting agent, and is mixed and smelted with the spent catalyst and a slag former to form a platinum group metal-rich iron alloy;

smelting a mixture of ferroalloy powder, a spent catalyst and a slag former at 1300-1600 ℃ for 30-180 min, and separating a slag phase from an iron phase to obtain the platinum group metal-rich ferroalloy and waste slag; the platinum group metal trapping rate is 90.0-99.7%, and the grade of the waste residue platinum group metal is less than or equal to 5 g/t;

the conditions for carrying out dehydration and deoiling on the acid-washing sludge are controlled as follows: the dehydration temperature is 100-120 ℃, and the dehydration time is 10-120 min; deoiling at 180-320 ℃ for 10-120 min;

controlling the mass ratio of the ferroalloy powder to the spent catalyst to the slagging agent to be as follows: 5-20 wt% of ferroalloy powder, 50-70 wt% of spent catalyst and 20-35 wt% of slagging agent, wherein the total weight of the ferroalloy powder, the spent catalyst and the slagging agent is 100 wt%.

2. The method for trapping platinum group metals in spent catalysts by using acid-washing sludge as claimed in claim 1, wherein the spent catalysts are crushed and then mixed with the ferroalloy powder and the slag former, and the particle size of the crushed spent catalysts is 0.1-20 mm;

the failure catalyst is one or more of failure automobile catalyst and failure chemical catalyst.

3. The method for capturing platinum group metals in spent catalysts according to claim 1 or 2, characterized in that the slag former comprises CaO and Na₂CO₃、CaF₂One or more of borax and borax;

in the mixture of the ferroalloy powder, the spent catalyst and the slag former, the addition amount of each component of the slag former is respectively CaO 15-30 wt% and Na₂CO₃ 0～20wt％、CaF₂0-5 wt% of borax and 0-5 wt%.

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