Method for recovering isooctene hydroformylation waste rhodium catalyst
By performing negative pressure distillation, calcination, ashing, dissolution, extraction and reduction treatment on isooctene hydroformylated waste rhodium catalyst, the problem of reduced catalyst activity is solved, and efficient rhodium recycling and economic advantages are achieved.
Patent Information
- Application Number
- CN202411786344.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-06
- Publication Date
- 2025-04-04
AI Technical Summary
The existing isooctene hydroformylation catalyst loses its catalytic activity after multiple recycling, resulting in waste of rhodium resources and increased production costs.
A method is used to recover the isooctene hydroformylation waste rhodium catalyst, including negative pressure distillation, high-temperature calcination and ashing of additives, concentrated hydrochloric acid dissolution and extraction, ion exchange adsorption, heating adjustment of pH and reduction treatment, and finally obtain high-purity rhodium powder.
The efficient recycling of waste rhodium catalysts has been achieved, with a rhodium recovery rate of 97%, reducing production costs and having significant economic advantages.
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Abstract
Description
Technical Field
[0001] The present application relates to the technical field of olefin hydroformylation catalyst recovery, and in particular to a method for recovering waste rhodium catalyst for isooctene hydroformylation. Background Art
[0002] Isooctene hydroformylation can produce isononanal (3,5,5-trimethyl-1-hexanal), which is an important organic chemical raw material, widely used in plasticizers, surfactants, fragrances, detergents and organic synthesis industries. From isononanal, many fine chemical products with high added value can be synthesized, especially isononanoic acid (3,5,5-trimethyl-1-hexanoic acid) can be obtained by oxidation. Due to the unique properties of high-branched isononanoic acid such as excellent wettability, permeability and emulsification, it has important uses in lubricants, industrial detergents and other industries.
[0003] Catalyst recovery refers to the process of separating precious metals from completely deactivated catalysts in the system and re-preparing them into fresh catalysts. This process is of great significance and great economic value for expensive rare metal catalysts. At present, the catalysts for isooctene hydroformylation only use rhodium and cobalt catalysts. Although cobalt is cheaper than rhodium, its catalytic activity is relatively low. Therefore, the catalyst is mainly rhodium catalyst. The rhodium catalyst in the isooctene hydroformylation process basically loses its catalytic activity after several cycles and cannot meet the activity standards required for production. Rhodium resources are scarce and expensive, and my country's rhodium mineral resources are scarce. Therefore, the value of recycling waste rhodium catalysts and preparing them into fresh rhodium catalysts is self-evident. Summary of the invention
[0004] The purpose of the present application is to overcome the deficiencies of the above-mentioned prior art and provide a method for recovering the waste rhodium catalyst for isooctene hydroformylation. The method of the present application is simple, convenient, has a high recovery rate (97%), and has obvious economic advantages for recovering the waste rhodium catalyst for isooctene hydroformylation.
[0005] To achieve the above purpose, the technical solution adopted by this application is:
[0006] In a first aspect, the present application provides a method for recovering a spent rhodium catalyst for isooctene hydroformylation, comprising the following steps:
[0007] 1) After the isooctene hydroformylation reaction is completed, the waste rhodium catalyst is distilled out under negative pressure;
[0008] 2) adding the additive to the waste rhodium catalyst in step 1) and mixing them evenly, calcining at high temperature (removing most of the organic matter), and cooling to obtain rhodium ash;
[0009] 3) using concentrated hydrochloric acid to dissolve the rhodium ash to obtain a rhodium ash solution, then adding an extractant to extract the rhodium ash solution (to remove uncalcined organic matter), and exchanging and adsorbing the obtained extract ions;
[0010] 4) heating the rhodium ash solution after the exchange adsorption in step 3), adjusting the pH, adding a reducing acid to obtain rhodium black, and then filtering, drying, and reducing to obtain rhodium powder;
[0011] The additive is a carbonate of an alkali metal or an alkaline earth metal.
[0012] In the technical solution of the present application, during the incineration and ashification process of the waste rhodium catalyst, a small amount of rhodium will be carried out as the organic impurities volatilize. Therefore, selecting a suitable additive can reduce the loss of rhodium carried over, and at the same time is beneficial to the ashification of the waste rhodium liquid, avoiding the formation of a large amount of insoluble charred materials that affect the recovery of rhodium.
[0013] The method of the present invention is relatively simple to operate, the conditions are easy to control, the efficiency is fast, and the recovery rate of rhodium is high. It is an effective means for recovering waste rhodium catalyst in the process of isooctene hydroformylation.
[0014] When carbonates of alkali metals or alkaline earth metals are used as additives, the recovery rate of rhodium can be increased.
[0015] As a preferred embodiment of the method for recovering the waste rhodium catalyst from isooctene hydroformylation described in the present application, the additive comprises CaCO 3 、NaCO 3 , CaCl 2 , Ca(OH) 2 , NaOH, KOH; preferably, the additive is KOH or Ca(OH) 2 .
[0016] By measuring the rhodium content after treatment, it was found that the dissolution of rhodium ash was easier when the above-mentioned additives were used. Especially when the additive was Ca(OH) 2 When using KOH or Rhodium ash, the rhodium ash dissolves better and the rhodium recovery rate is higher.
[0017] Preferably, in step 1), the negative pressure is -0.5 MPa to -0.1 MPa; and the distillation temperature is 80 to 150°C.
[0018] As a preferred embodiment of the method for recovering waste rhodium catalyst from isooctene hydroformylation described in the present application, in the step 2), the mass ratio of the additive to the waste rhodium catalyst is 1:2 to 5:4; the mass ratio is preferably 1: 1. When the mass ratio of the additive to the waste rhodium catalyst is within the above range, the recovery rate of rhodium can be effectively improved.
[0019] As a preferred embodiment of the method for recovering waste rhodium catalyst from isooctene hydroformylation described in the present application, in the step 2), the ashing temperature is 200°C to 800°C, and the ashing time is 2h to 5h. Preferably, the ashing temperature is 600°C, and the ashing time is 3h.
[0020] The use of the ashing temperature and ashing time within the above range can effectively improve the recovery rate of rhodium.
[0021] As a preferred embodiment of the method for recovering waste rhodium catalyst from isooctene hydroformylation described in the present application, the concentration of the concentrated hydrochloric acid is 36% to 38%.
[0022] As a preferred embodiment of the method for recovering waste rhodium catalyst from isooctene hydroformylation described in the present application, the usage ratio of concentrated hydrochloric acid to rhodium ash is (10 mL to 50 mL): 5 g, preferably 30 ml: 5 g.
[0023] When the amount of hydrochloric acid is too low, the rhodium ash cannot be completely dissolved, resulting in a low rhodium recovery rate; as the amount of hydrochloric acid increases, the recovery rate increases accordingly; when the amount of hydrochloric acid is too high, the rhodium ash is completely dissolved and the rhodium recovery rate does not change. When the amount of hydrochloric acid is within an appropriate range, the rhodium recovery rate can be effectively improved.
[0024] As a preferred embodiment of the method for recovering waste rhodium catalyst from isooctene hydroformylation described in the present application, in step 3), concentrated hydrochloric acid is used to dissolve rhodium ash at a temperature of 15° C. to 50° C., preferably, the dissolution temperature is 30° C. Preferably, the dissolution time is 1 to 9 hours, preferably, the dissolution time is 5 hours.
[0025] When the temperature is low, the rhodium ash cannot be completely dissolved, and the rhodium recovery rate is low. As the temperature rises, the rhodium recovery rate is significantly improved, but too high a temperature will increase the volatilization of hydrochloric acid. When the dissolution temperature and time of the present application are used in the above range, the rhodium ash can be completely dissolved, the rhodium recovery rate is high, and the volatilization of hydrochloric acid will not be increased.
[0026] As a preferred embodiment of the method for recovering waste rhodium catalyst from isooctene hydroformylation described in the present application, the extractant includes at least one of ethyl acetate, tributyl phosphate and n-pentanol. Preferably, the extractant is tributyl phosphate.
[0027] As a preferred embodiment of the method for recovering the waste rhodium catalyst from isooctene hydroformylation described in the present application, the ratio of the extractant to the rhodium ash solution is 1:2 to 2:1, and the extraction temperature is 15 to 50° C. Preferably, the ratio of the extractant to the rhodium ash solution is 1 to 1, and the extraction temperature is 20° C.
[0028] Preferably, the ion exchange uses ion exchange resin, more preferably cation exchange resin. The cation exchange resin includes iminodiacetic acid cation exchange resin to remove other base metal ions.
[0029] As a preferred embodiment of the method for recovering spent rhodium catalyst from isooctene hydroformylation described in the present application, in the step 4), the heating temperature is 80°C.
[0030] Preferably, in the step 4), an alkali solution is used to adjust the pH, the alkali solution is sodium hydroxide, and the pH=5.
[0031] Preferably, in step 4), the reducing acid is formic acid.
[0032] Preferably, in step 4), reduction is carried out under a hydrogen atmosphere, the hydrogen reduction temperature is 800° C., and the reduction time is 3 h.
[0033] Compared with the prior art, this application has the following beneficial effects:
[0034] The present application provides a method for recovering waste rhodium catalyst from isooctene hydroformylation. The method is simple and convenient, and the process conditions such as the type and amount of additives, ashing temperature, amount of concentrated hydrochloric acid, dissolution temperature and time are investigated and optimized, which greatly improves the recovery rate of rhodium and has certain advantages in production costs. DETAILED DESCRIPTION
[0035] In order to better illustrate the purpose, technical solutions and advantages of the present application, the present application will be further described below in conjunction with specific embodiments.
[0036] In the following examples, the experimental methods used are conventional methods unless otherwise specified, and the materials, reagents, etc. used are all commercially available unless otherwise specified.
[0037] Example 1: Effect of different additives on the recovery of rhodium
[0038] This embodiment provides a method for recovering a spent rhodium catalyst for isooctene hydroformylation, comprising the following steps:
[0039] 1) After the isooctene hydroformylation reaction is completed, the waste rhodium catalyst is distilled out under a certain negative pressure, the negative pressure is -0.5Mpa to -0.1Mpa, and the distillation temperature is 80 to 150° C.;
[0040] 2) Take 10g of waste rhodium catalyst and add different additives (Ca(OH) 2 、NaCO 3、 CaCl 2 , KOH, NaOH, CaCO 3) are added to the waste rhodium catalyst in step 1) and mixed evenly (the mass ratio of the additive to the waste rhodium catalyst is 1:1), calcined in a crucible at high temperature to remove most of the organic matter, the ash temperature is 600° C., the ash time is 3 h, and cooled to obtain rhodium ash;
[0041] 3) Take 5g of the above-mentioned rhodium ash, use concentrated hydrochloric acid (concentration is 36% ~ 38%) to dissolve the rhodium ash (the amount ratio of concentrated hydrochloric acid to rhodium ash is 30mL:5g), dissolution time 5h, dissolution temperature 30 ℃, make rhodium ash solution, then add tributyl phosphate to extract the rhodium ash solution (the amount ratio of tributyl phosphate and rhodium ash solution is 10mL:10mL), remove the organic matter that is not roasted, the temperature of extraction is 20 ℃, the extract ions obtained are treated with iminodiacetic acid-based cation exchange resin, adsorb base metal cations, and other impurities in the rhodium solution are thoroughly removed;
[0042] 4) heating the rhodium ash solution after the exchange adsorption in step 3) (temperature is 80° C.), adding to adjust the pH, adding reducing acid (formic acid), continuously adding alkali solution (sodium hydroxide) during the reduction process to maintain the pH (PH=5) unchanged, and boiling to obtain reduced rhodium black, then filtering, washing with pure water, drying, and reducing under a hydrogen atmosphere (temperature is 800° C., reduction time is 3 h), and determining the rhodium content therein by a right-handed optical mirror photometer to obtain rhodium powder with a purity of up to 99% (when the additive is Ca(OH) 2 hour).
[0043] Table 1 Effect of additives
[0044]
[0045] As can be seen from Table 1, by measuring the rhodium content after treatment, it was found that the use of Ca(OH) 2 Or when KOH is used as an additive, the rhodium ash is easier to dissolve, the unit catalyst after treatment contains higher rhodium, and the rhodium recovery rate is higher.
[0046] Example 2: Effect of different amounts of additives on the recovery of rhodium
[0047] This embodiment provides a method for recovering a spent rhodium catalyst for isooctene hydroformylation, comprising the following steps:
[0048] 1) After the isooctene hydroformylation reaction is completed, the waste rhodium catalyst is distilled out under a certain negative pressure, the negative pressure is -0.5Mpa to -0.1Mpa, and the distillation temperature is 80 to 150° C.;
[0049] 2) Take 10g of waste rhodium catalyst and add the additive Ca(OH) 2The waste rhodium catalyst added to step 1) is mixed evenly (the mass ratio of the additive to the waste rhodium catalyst is set to 2:1, 5:3, 5:4, 1:1, and 5:6, respectively), calcined in a crucible at high temperature to remove most of the organic matter, the ash temperature is 600° C., the ash time is 3 h, and the rhodium ash is obtained by cooling;
[0050] 3) Take 5g of the above-mentioned rhodium ash, use concentrated hydrochloric acid (concentration is 36% ~ 38%) to dissolve the rhodium ash (the amount ratio of concentrated hydrochloric acid to rhodium ash is 30mL:5g), dissolution time 5h, dissolution temperature 30 ℃, make rhodium ash solution, then add tributyl phosphate to extract the rhodium ash solution (the amount ratio of tributyl phosphate and rhodium ash solution is 10mL:10mL), remove the organic matter that is not roasted, the temperature of extraction is 20 ℃, the extract ions obtained are treated with iminodiacetic acid-based cation exchange resin, adsorb base metal cations, and other impurities in the rhodium solution are thoroughly removed;
[0051] 4) heating the rhodium ash solution after the exchange adsorption in step 3) (temperature is 80° C.), adding to adjust the pH, adding reducing acid (formic acid), continuously adding alkali solution (sodium hydroxide) during the reduction process to maintain the pH (PH=5) unchanged, and boiling to obtain reduced rhodium black, which is then filtered, washed with pure water, dried, and reduced in a hydrogen atmosphere (temperature is 800° C., reduction time is 3 h) to obtain rhodium powder.
[0052] Table 2 Effect of additive dosage
[0053]
[0054] As can be seen from Table 2, by measuring the rhodium content after treatment, it was found that the use of Ca(OH) 2 It is an additive, the mass of the additive and the waste rhodium catalyst is 1:1, and the unit catalyst after treatment contains a higher rhodium content.
[0055] Example 3: Effect of ashing temperature on rhodium recovery
[0056] This embodiment provides a method for recovering a spent rhodium catalyst for isooctene hydroformylation, comprising the following steps:
[0057] 1) After the isooctene hydroformylation reaction is completed, the waste rhodium catalyst is distilled out under a certain negative pressure, the negative pressure is -0.5Mpa to -0.1Mpa, and the distillation temperature is 80 to 150° C.;
[0058] 2) Take 10g of waste rhodium catalyst and add the additive Ca(OH) 2The waste rhodium catalyst added to step 1) is mixed evenly (the mass ratio of the additive to the waste rhodium catalyst is 1:1), and most of the organic matter is removed by high-temperature roasting in a crucible, the high-temperature roasting temperature is set to 200°C, 400°C, 600°C, 800°C, and 1000°C, respectively, and the high-temperature roasting time is 3h, and the rhodium ash is obtained by cooling;
[0059] 3) Take 5g of the above-mentioned rhodium ash, use concentrated hydrochloric acid (concentration is 36% ~ 38%) to dissolve the rhodium ash (the amount ratio of concentrated hydrochloric acid to rhodium ash is 30mL:5g), dissolution time 5h, dissolution temperature 30 ℃, make rhodium ash solution, then add tributyl phosphate to extract the rhodium ash solution (the amount ratio of tributyl phosphate and rhodium ash solution is 10mL:10mL), remove the organic matter that is not roasted, the temperature of extraction is 20 ℃, the extract ions obtained are treated with iminodiacetic acid-based cation exchange resin, adsorb base metal cations, and other impurities in the rhodium solution are thoroughly removed;
[0060] 4) heating the rhodium ash solution after the exchange adsorption in step 3) (temperature is 80° C.), adding to adjust the pH, adding reducing acid (formic acid), continuously adding alkali solution (sodium hydroxide) during the reduction process to maintain the pH (PH=5) unchanged, and boiling to obtain reduced rhodium black, which is then filtered, washed with pure water, dried, and reduced in a hydrogen atmosphere (temperature is 800° C., reduction time is 3 h) to obtain rhodium powder.
[0061] Table 3 Effect of ashing temperature
[0062]
[0063] As shown in Table 3, after ICP determination, it was found that the use of Ca(OH) 2 As an additive, when the ashing temperature is 200℃~900℃, the rhodium content of the unit catalyst after treatment is higher, among which 600℃ is the best calcination temperature.
[0064] Example 4: Effect of Dissolution Time of Hydrochloric Acid on Recovery of Rhodium
[0065] This embodiment provides a method for recovering a spent rhodium catalyst for isooctene hydroformylation, comprising the following steps:
[0066] 1) After the isooctene hydroformylation reaction is completed, the waste rhodium catalyst is distilled out under a certain negative pressure, the negative pressure is -0.5Mpa to -0.1Mpa, and the distillation temperature is 80 to 150° C.;
[0067] 2) Take 10g of waste rhodium catalyst and add the additive Ca(OH) 2The waste rhodium catalyst added to step 1) is mixed evenly (the mass ratio of the additive to the waste rhodium catalyst is 1:1), and most of the organic matter is removed by high-temperature roasting in a crucible at a temperature of 600° C. for 3 hours, and then cooled to obtain rhodium ash;
[0068] 3) take 5g of the above-mentioned rhodium ash, use concentrated hydrochloric acid (concentration is 36% ~ 38%) to dissolve the rhodium ash (the amount ratio of concentrated hydrochloric acid and rhodium ash is 30mL:5g), dissolution time is set to 1h, 3h, 5h, 7h, 9h respectively, dissolution temperature is 30 ℃, make rhodium ash solution, then add tributyl phosphate to extract the rhodium ash solution (the amount ratio of tributyl phosphate and rhodium ash solution is 10mL:10mL), remove the organic matter that is not roasted, the temperature of extraction is 20 ℃, the extract ion obtained adopts iminodiacetic acid group cation exchange resin to handle, adsorb base metal cations, and other impurities in the rhodium solution are thoroughly removed;
[0069] 4) heating the rhodium ash solution after the exchange adsorption in step 3) (temperature is 80° C.), adding to adjust the pH, adding reducing acid (formic acid), continuously adding alkali solution (sodium hydroxide) during the reduction process to maintain the pH (PH=5) unchanged, and boiling to obtain reduced rhodium black, which is then filtered, washed with pure water, dried, and reduced in a hydrogen atmosphere (temperature is 800° C., reduction time is 3 h) to obtain rhodium powder.
[0070] Table 4 Effect of dissolution time
[0071]
[0072] As can be seen from Table 4, after 1 hour of dissolution, the rhodium ash is not completely dissolved, and the rhodium recovery rate increases with the extension of the dissolution time. When the dissolution time exceeds 5 hours, the rhodium recovery tends to be stable. Therefore, preferably, the dissolution time is 5 hours.
[0073] Example 5: Effect of hydrochloric acid dosage on rhodium recovery
[0074] This embodiment provides a method for recovering a spent rhodium catalyst for isooctene hydroformylation, comprising the following steps:
[0075] 1) After the isooctene hydroformylation reaction is completed, the waste rhodium catalyst is distilled out under a certain negative pressure, the negative pressure is -0.5Mpa to -0.1Mpa, and the distillation temperature is 80 to 150° C.;
[0076] 2) Take 10g of waste rhodium catalyst and add the additive Ca(OH) 2 The waste rhodium catalyst added to step 1) is mixed evenly (the mass ratio of the additive to the waste rhodium catalyst is 1:1), and most of the organic matter is removed by high-temperature roasting in a crucible at a temperature of 600° C. for 3 hours, and then cooled to obtain rhodium ash;
[0077] 3) take 5g of above-mentioned rhodium ash, use concentrated hydrochloric acid (concentration is 36%~38%) to dissolve the rhodium ash (the amount ratio of concentrated hydrochloric acid and rhodium ash is set at 100mL:5g, 20mL:5g, 30mL:5g, 40mL:5g, 50mL:5g respectively), dissolution time is 5h, dissolution temperature is 30 ℃, make rhodium ash solution, then add tributyl phosphate to extract the rhodium ash solution (the amount ratio of tributyl phosphate and rhodium ash solution is 10mL:10mL), remove the organic matter that is not roasted, the temperature of extraction is 20 ℃, the extract ion obtained adopts iminodiacetic acid group cation exchange resin to handle, adsorb base metal cations, and other impurities in the rhodium solution are thoroughly removed;
[0078] 4) heating the rhodium ash solution after the exchange adsorption in step 3) (temperature is 80° C.), adding to adjust the pH, adding reducing acid (formic acid), continuously adding alkali solution (sodium hydroxide) during the reduction process to maintain the pH (PH=5) unchanged, and boiling to obtain reduced rhodium black, which is then filtered, washed with pure water, dried, and reduced in a hydrogen atmosphere (temperature is 800° C., reduction time is 3 h) to obtain rhodium powder.
[0079] Table 5 Effect of hydrochloric acid dosage
[0080]
[0081] As can be seen from Table 5, when the amount of hydrochloric acid used is in a ratio of (20-50) mL:5 g to the amount of rhodium ash, the unit catalyst after treatment contains higher rhodium. Preferably, the amount of hydrochloric acid used is in a ratio of 30 mL:5 g to the amount of rhodium ash.
[0082] Example 6: Effect of hydrochloric acid dissolution temperature on rhodium recovery
[0083] This embodiment provides a method for recovering a spent rhodium catalyst for isooctene hydroformylation, comprising the following steps:
[0084] 1) After the isooctene hydroformylation reaction is completed, the waste rhodium catalyst is distilled out under a certain negative pressure, the negative pressure is -0.5Mpa to -0.1Mpa, and the distillation temperature is 80 to 150° C.;
[0085] 2) Take 10g of waste rhodium catalyst and add the additive Ca(OH) 2 The waste rhodium catalyst added to step 1) is mixed evenly (the mass ratio of the additive to the waste rhodium catalyst is 1:1), and most of the organic matter is removed by high-temperature roasting in a crucible at a temperature of 600° C. for 3 hours, and then cooled to obtain rhodium ash;
[0086] 3) Take 5g of the above-mentioned rhodium ash, use concentrated hydrochloric acid (concentration is 36% ~ 38%) to dissolve the rhodium ash (the amount ratio of concentrated hydrochloric acid to rhodium ash is 30mL:5g), the dissolution time is 5h, and the dissolution temperature is set at 15 ℃, 20 ℃, 30 ℃, 40 ℃, 50 ℃ respectively, to obtain a rhodium ash solution, then add tributyl phosphate to extract the rhodium ash solution (the amount ratio of tributyl phosphate and rhodium ash solution is 10mL:10mL), remove the organic matter that is not roasted, the temperature of extraction is 20 ℃, the extract ions obtained are processed by iminodiacetic acid-based cation exchange resin, adsorb base metal cations, and other impurities in the rhodium solution are thoroughly removed;
[0087] 4) heating the rhodium ash solution after the exchange adsorption in step 3) (temperature is 80° C.), adding to adjust the pH, adding reducing acid (formic acid), continuously adding alkali solution (sodium hydroxide) during the reduction process to maintain the pH (PH=5) unchanged, and boiling to obtain reduced rhodium black, which is then filtered, washed with pure water, dried, and reduced in a hydrogen atmosphere (temperature is 800° C., reduction time is 3 h) to obtain rhodium powder.
[0088] Table 6 Effect of hydrochloric acid dissolution temperature
[0089]
[0090] It can be seen from Table 6 that when concentrated hydrochloric acid dissolves rhodium ash at a dissolution temperature of 30-50°C, the unit catalyst after treatment contains more rhodium and the recovery rate of rhodium is higher.
[0091] Example 7: Effect of Extractant on Rhodium Recovery
[0092] This embodiment provides a method for recovering a spent rhodium catalyst for isooctene hydroformylation, comprising the following steps:
[0093] 1) After the isooctene hydroformylation reaction is completed, the waste rhodium catalyst is distilled out under a certain negative pressure, the negative pressure is -0.5Mpa to -0.1Mpa, and the distillation temperature is 80 to 150° C.;
[0094] 2) Take 10g of waste rhodium catalyst and add the additive Ca(OH) 2 The waste rhodium catalyst added to step 1) is mixed evenly (the mass ratio of the additive to the waste rhodium catalyst is 1:1), and most of the organic matter is removed by high-temperature roasting in a crucible at a temperature of 600° C. for 3 hours, and then cooled to obtain rhodium ash;
[0095] 3) Take 5g of the above-mentioned rhodium ash, use concentrated hydrochloric acid (concentration is 36% ~ 38%) to dissolve the rhodium ash (the amount ratio of concentrated hydrochloric acid to rhodium ash is 30mL:5g), the dissolution time is 5h, and the dissolution temperature is set at 15 ℃, 20 ℃, 30 ℃, 40 ℃, 50 ℃ respectively, to obtain a rhodium ash solution, then add different extractants (ethyl acetate, n-amyl alcohol, tributyl phosphate) to extract the rhodium ash solution (the amount ratio of tributyl phosphate and rhodium ash solution is 10mL:10mL), remove the organic matter that is not roasted, the extraction temperature is 20 ℃, the extraction ratio is 1, the extract ions obtained are treated with iminodiacetic acid-based cation exchange resin, adsorb base metal cations, and other impurities in the rhodium solution are thoroughly removed;
[0096] 4) heating the rhodium ash solution after the exchange adsorption in step 3) (temperature is 80° C.), adding to adjust the pH, adding reducing acid (formic acid), continuously adding alkali solution (sodium hydroxide) during the reduction process to maintain the pH (PH=5) unchanged, and boiling to obtain reduced rhodium black, which is then filtered, washed with pure water, dried, and reduced in a hydrogen atmosphere (temperature is 800° C., reduction time is 3 h) to obtain rhodium powder.
[0097] Table 7 Selection of extraction agent
[0098]
[0099] As can be seen from Table 7, the extractant of the gray rhodium solution is tributyl phosphate, and a large amount of rhodium is recovered in the liquid phase.
[0100] Example 8: Effect of the amount of extractant on the recovery of rhodium
[0101] This embodiment provides a method for recovering a spent rhodium catalyst for isooctene hydroformylation, comprising the following steps:
[0102] 1) After the isooctene hydroformylation reaction is completed, the waste rhodium catalyst is distilled out under a certain negative pressure, the negative pressure is -0.5Mpa to -0.1Mpa, and the distillation temperature is 80 to 150° C.;
[0103] 2) Take 10g of waste rhodium catalyst and add the additive Ca(OH) 2 The waste rhodium catalyst added to step 1) is mixed evenly (the mass ratio of the additive to the waste rhodium catalyst is 1:1), and most of the organic matter is removed by high-temperature roasting in a crucible at a temperature of 600° C. for 3 hours, and then cooled to obtain rhodium ash;
[0104] 3) Take 5g of the above-mentioned rhodium ash, use concentrated hydrochloric acid (concentration is 36% ~ 38%) to dissolve the rhodium ash (the amount ratio of concentrated hydrochloric acid to rhodium ash is 30mL:5g), the dissolution time is 5h, and the dissolution temperature is set at 15 ℃, 20 ℃, 30 ℃, 40 ℃, 50 ℃ respectively, to obtain a rhodium ash solution, then add tributyl phosphate to extract the rhodium ash solution (the amount ratio of tributyl phosphate and rhodium ash solution is set at 10mL:10mL, 15mL:10mL, 20mL:10mL respectively), remove the organic matter that is not roasted, the temperature of extraction is 20 ℃, the extraction ratio is 1, the extract ions obtained are processed with iminodiacetic acid-based cation exchange resin, adsorb base metal cations, and other impurities in the rhodium solution are thoroughly removed;
[0105] 4) heating the rhodium ash solution after the exchange adsorption in step 3) (temperature is 80° C.), adding to adjust the pH, adding reducing acid (formic acid), continuously adding alkali solution (sodium hydroxide) during the reduction process to maintain the pH (PH=5) unchanged, and boiling to obtain reduced rhodium black, which is then filtered, washed with pure water, dried, and reduced in a hydrogen atmosphere (temperature is 800° C., reduction time is 3 h) to obtain rhodium powder.
[0106] Table 8 Selection of extraction agent dosage
[0107]
[0108] It can be seen from Table 8 that when the ratio of the gray rhodium solution to the extractant tributyl phosphate is 1:1, a larger amount of rhodium is recovered in the liquid phase.
[0109] Example 9: Effect of extraction temperature on rhodium recovery
[0110] This embodiment provides a method for recovering a spent rhodium catalyst for isooctene hydroformylation, comprising the following steps:
[0111] 1) After the isooctene hydroformylation reaction is completed, the waste rhodium catalyst is distilled out under a certain negative pressure, the negative pressure is -0.5Mpa to -0.1Mpa, and the distillation temperature is 80 to 150° C.;
[0112] 2) Take 10g of waste rhodium catalyst and add the additive Ca(OH) 2 The waste rhodium catalyst added to step 1) is mixed evenly (the mass ratio of the additive to the waste rhodium catalyst is 1:1), and most of the organic matter is removed by high-temperature roasting in a crucible at a temperature of 600° C. for 3 hours, and then cooled to obtain rhodium ash;
[0113] 3) Take 5g of the above-mentioned rhodium ash, use concentrated hydrochloric acid (concentration is 36% ~ 38%) to dissolve the rhodium ash (the amount ratio of concentrated hydrochloric acid and rhodium ash is 30mL:5g), the dissolution time is 5h, and the dissolution temperature is set at 15 ℃, 20 ℃, 30 ℃, 40 ℃, 50 ℃ respectively, to obtain a rhodium ash solution, then add tributyl phosphate to extract the rhodium ash solution (the amount ratio of tributyl phosphate and rhodium ash solution is set at 10mL:10mL, 15mL:10mL, 20mL:10mL respectively), remove the organic matter that is not roasted, the temperature of extraction is set at 15 ℃, 20 ℃, 30 ℃, 40 ℃, 50 ℃ respectively, the extraction ratio is 1, the extract ions obtained are processed with iminodiacetic acid-based cation exchange resin, adsorb base metal cations, and other impurities in the rhodium solution are thoroughly removed;
[0114] 4) heating the rhodium ash solution after the exchange adsorption in step 3) (temperature is 80° C.), adding to adjust the pH, adding reducing acid (formic acid), continuously adding alkali solution (sodium hydroxide) during the reduction process to maintain the pH (PH=5) unchanged, and boiling to obtain reduced rhodium black, which is then filtered, washed with pure water, dried, and reduced in a hydrogen atmosphere (temperature is 800° C., reduction time is 3 h) to obtain rhodium powder.
[0115] Table 9 Effect of extraction temperature
[0116]
[0117]
[0118] As can be seen from Table 9, when the extraction temperature is 20°C, a large amount of rhodium is recovered in the liquid phase, and the extraction temperature is preferably 20-50°C.
[0119] The present application relates to a method for recovering waste rhodium catalyst in the process of isooctene hydroformylation. After process optimization, high-purity rhodium powder can be obtained. Rhodium powder can be used to synthesize fresh rhodium catalyst for isooctene hydroformylation reaction. The method is simple, convenient, has a high recovery rate (up to 97%), and has obvious economic advantages.
[0120] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present application rather than to limit the scope of protection of the present application. Although the present application has been described in detail with reference to the preferred embodiments, ordinary technicians in this field should understand that the technical solution of the present application can be modified or replaced by equivalents without departing from the essence and scope of the technical solution of the present application.
Claims
1. A method for recovering waste rhodium catalyst from isooctene hydroformylation, characterized in that: The following steps are involved: 1) After the isooctene hydroformylation reaction is completed, the waste rhodium catalyst is distilled out under negative pressure; 2) adding the additive to the waste rhodium catalyst in step 1) and mixing evenly, calcining at high temperature, and cooling to obtain rhodium ash; 3) using concentrated hydrochloric acid to dissolve the rhodium ash to obtain a rhodium ash solution, then adding an extractant to extract the rhodium ash solution, and subjecting the obtained extract to ion exchange adsorption; 4) heating the rhodium ash solution after the exchange adsorption in step 3), adjusting the pH, adding a reducing acid to obtain rhodium black, and then filtering, drying, and reducing to obtain rhodium powder; The additive is a carbonate of an alkali metal or an alkaline earth metal.
2. The method for recovering the waste rhodium catalyst from isooctene hydroformylation as claimed in claim 1, wherein: The additive includes CaCO3, NaCO3, CaCl2, Ca(OH)2, NaOH, KOH; preferably, the additive is KOH or Ca(OH)2.
3. The method for recovering the waste rhodium catalyst from isooctene hydroformylation as claimed in claim 1, characterized in that: In the step 2), the mass ratio of the additive to the waste rhodium catalyst is 1:2 to 5:4; the mass ratio is preferably 1:
1.
4. The method for recovering the waste rhodium catalyst from isooctene hydroformylation as claimed in claim 1, characterized in that: In the step 2), the ashing temperature is 200° C. to 800° C., and the ashing time is 2 h to 5 h.
5. The method for recovering the waste rhodium catalyst from isooctene hydroformylation as claimed in claim 1, characterized in that: The concentration of the concentrated hydrochloric acid is 36% to 38%.
6. The method for recovering the waste rhodium catalyst from isooctene hydroformylation as claimed in claim 1, characterized in that: The usage ratio of the concentrated hydrochloric acid to the rhodium ash is (10 mL to 50 mL): 5 g.
7. The method for recovering the waste rhodium catalyst from isooctene hydroformylation as claimed in claim 1, characterized in that: In the step 3), concentrated hydrochloric acid is used to dissolve the rhodium ash at a temperature of 15°C to 50°C, preferably, the dissolution temperature is 30°C.
8. The method for recovering the waste rhodium catalyst from isooctene hydroformylation as claimed in claim 1, characterized in that: The extractant comprises at least one of ethyl acetate, tributyl phosphate and n-pentanol. Preferably, the extractant is tributyl phosphate.
9. The method for recovering the waste rhodium catalyst from isooctene hydroformylation as claimed in claim 1, characterized in that: The dosage ratio of the extractant to the rhodium ash solution is 1:2 to 2:1, and the extraction temperature is 15 to 50°C.
10. The method for recovering the waste rhodium catalyst from isooctene hydroformylation as claimed in claim 1, characterized in that: In the step 4), the heating temperature is 80°C.