Rhodium-based catalysts, their preparation and use

Abstract

The application discloses a rhodium-based catalyst and a preparation method and application thereof. The preparation method comprises the following steps: (1) placing a functionalized silica gel material in a rhodium-containing solution, adsorbing under stirring, and then filtering and washing to obtain a rhodium-loaded functionalized silica gel material; (2) preparing graphene oxide; (3) adding a solvent, a vulcanizing agent and an emulsifier into the rhodium-loaded functionalized silica gel material obtained in the step (1) to obtain a mixture through first stirring; mixing the graphene oxide obtained in the step (2) with water and performing ultrasonic dispersion, adding into the mixture, second stirring, and then performing shearing to obtain a mixed emulsion; adding a reducing agent, heating, washing, drying and vulcanizing to obtain the rhodium-based catalyst. The catalyst obtained through the method can effectively improve the conversion rate in an olefin hydroformylation reaction, and can also realize efficient recovery of rhodium in low-concentration rhodium-containing waste liquid, thereby reducing production cost.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of catalyst preparation, in particular to a rhodium-based catalyst and its preparation method and application. BACKGROUND

[0002] Olefins hydroformylation reaction, also known as OXO reaction, refers to the reaction of olefins with carbon monoxide and hydrogen under the action of transition metal complex catalyst to generate normal and isomeric aldehydes with one more carbon atom than the raw material olefins.

[0003] Olefins hydroformylation reaction is a typical homogeneous complex catalytic reaction, which has the advantages of high catalyst activity and good selectivity, and is often used in industry to produce aldehydes and alcohols widely used in the field of fine chemicals, which can be used to synthesize surfactants, fabric additives and plasticizers, and also can be used to produce various pharmaceutical intermediates for the pharmaceutical industry, and can be further processed into fragrances for the food industry. Olefins hydroformylation reaction is an atomic economic reaction, in which all atoms in synthesis gas enter into the olefins, without waste and toxic and harmful substances generated to the environment, which is a recognized green chemical process and meets the requirements of sustainable development, and has become a key development of chemical industry and a key research field at home and abroad.

[0004] In the mid-1950s, it was found that rhodium is more active in hydroformylation reaction than cobalt, and the United Carbon Corporation (UCC) of the United States, the DAVY Power Gas Company of the United Kingdom and the Johnson Matthey Company jointly developed an oil-soluble rhodium phosphine complex HRh(CO)(P(Ph3)3) catalyst. Compared with cobalt-based catalyst, the rhodium-based catalyst has low operating pressure and good safety, and is called low-pressure OXO process. However, due to the fact that rhodium is a noble metal, the catalyst is difficult to recover, and thus the popularization and application of the catalyst are limited.

[0005] China is very short of platinum group metal mineral resources, and the reserves of platinum group metals are small. With the rapid development of modern industry and science and technology, the consumption of platinum group metals has increased significantly. The rhodium platinum group metal recycling industry in China started later than that in foreign countries, but developed rapidly. While developing rapidly, there are many deficiencies, among which the backward recovery process technology, the serious environmental pollution and resource waste caused in the refining process have become problems to be solved in the recovery process. SUMMARY

[0006] In view of the above deficiencies in the prior art, the present application provides a rhodium-based catalyst and its preparation method and application. The catalyst obtained by the method is used in olefins hydroformylation reaction, which can effectively improve the conversion rate of the reaction.

[0007] The first aspect of the present application provides a preparation method of a rhodium-based catalyst, comprising the following steps:

[0008] (1) placing the functionalized silica gel material into a rhodium-containing solution, adsorbing under stirring, and then filtering and washing to obtain a functionalized silica gel material loaded with rhodium;

[0009] (2) preparing graphene oxide;

[0010] (3) adding a solvent, a vulcanizing agent and an emulsifier to the functionalized silica gel material loaded with rhodium obtained in step (1) to obtain a mixture; mixing the graphene oxide obtained in step (2) with water and performing ultrasonic dispersion, and then adding to the mixture, stirring again, and then shearing to obtain a mixed emulsion; adding a reducing agent, heating, washing, drying and vulcanizing to obtain a rhodium-based catalyst.

[0011] Further, in step (1), the rhodium-containing solution is a conventional rhodium-containing solution in the art, and is preferably a rhodium-containing waste liquid. In the rhodium-containing solution, the rhodium source is preferably at least one of triphenylphosphine acetylacetone rhodium, rhodium trichloride, rhodium iodide, acetylacetone rhodium, etc.

[0012] Further, the rhodium-containing waste liquid is mainly derived from at least one of rhodium smelting, medicine and intermediate purification, three-way catalyst waste, rhodium-catalyzed organic reaction process streams or waste liquids, etc.

[0013] Further, in step (1), the mass concentration of rhodium in the rhodium-containing solution is 300 ppm to 2000 ppm.

[0014] Further, in step (1), the functionalized silica gel material and its preparation method are described in CN110191911B, the entire content of which is incorporated herein by reference. The functionalized silica gel material has the structure shown in general formula I.

[0015] Further, in step (1), the functionalized silica gel material has the structure shown in general formula I: [Y] y [A] a [B 1 ] 1b [B 2 ] 2b [C 1 ] 1c [C 2 ] 2c [C 3 ] 3c [C 4 ] 4c [D 1 ] 1d [D 2 ] 2d [D 3 ] 3d [D4 ] 4d [D 5 ] 5d [D 6 ] 6d [E] e [F] f [G] g [H] h [J] j [K] k [M] m [P] p [U] u [V] v [W] w [X] x ,

[0016] wherein Y is Si(O 4 / 2 ) ; W is R z R 1 Si(O q / 2 ) ; X is (O 3 / 2 )SiC3H6SH;

[0017] A is

[0018] [(O 3 / 2 )Si(CH2)2SCH2CH2S-CH2CH2CH2SR] a1 [(O 3 / 2 )Si(CH2)2SCH2CH2SCH2CH2CH2S(CH2)2Si(O 3 / 2 )] a2 [(O 3 / 2 )Si(CH2)2SCH2CH2CH2SCH2CH2SR] a3 ;

[0019] B 1 is

[0020] [(O 3 / 2 )Si(CH2)3SCH2CH2[H2SH] b1 [(O 3 / 2 )Si(CH2)2SCH2CH2CH2SCH2CH2SH] b2 [(O 3 / 2 )Si(CH2)3SCH2CH2CH2SCH2CH2SCH2CH2CH2S(CH2)3Si(O 3 / 2 )] b3 :

[0021] B 2 is

[0022] [(O3 / 2 )Si(CH2)3SCH2CH2CH2SH] b1 [(O 3 / 2 )Si(CH2)3SCH2CH2CH2SCH2CH2CH2SH] b2 [(O 3 / 2 )Si(CH2)3SCH2CH2CH2SCH2CH2CH2SCH2CH2CH2S(CH2)3Si(O 3 / 2 ] b3 ;

[0023] C 1 is

[0024] [(O 3 / 2 )Si(CH2)2SCH2CH2SCH2CH2SCH2CH2SH] c1 [(O 3 / 2 )Si(CH2)2SCH2CH2SCH2CH2SCH2CH2S(CH2)2Si(O 3 / 2 )] c2 ;

[0025] C 2 is

[0026] [(O 3 / 2 )Si(CH2)2SCH2CH2CH2S-CH2CH2SCH2CH2CH2SH] c1 [(O 3 / 2)Si(CH2)2SCH2CH2CH2SCH2CH2SCH2CH2CH2S(CH2)2Si(O 3 / 2 )] c2 ;

[0027] C 3 is

[0028] [(O 3 / 2 )Si(CH2)3SCH2CH2CH2SCH2CH2SCH2CH2CH2SR] c1 [(O 3 / 2 )Si(CH2)3SCH2CH2CH2SCH2CH2S-CH2CH2CH2S(CH2)3Si(O 3 / 2 )] c2 ;

[0029] C 4 is

[0030] [(O 3 / 2 )Si(CH2)3SCH2CH2CH2SCH2CH2CH2SCH2CH2CH2SR]c1 [(O 3 / 2 )Si(CH2)3SCH2CH2CH2SCH2CH2CH2SCH2CH2CH2S(CH2)3Si(O 3 / 2 ] c2 ;

[0031] D 1 is

[0032] [(O 3 / 2 )Si(CH2)2SCH2CH2SCH2CH2CH2SH] d1 [(O 3 / 2 )Si(CH2)2SCH2CH2S(CH2)2Si(O 3 / 2 ] d2 ;

[0033] D 2 is

[0034] [(O 3 / 2 )Si(CH2)2SCH2CH2CH2SCH2CH2CH2SH] d1 [(O 3 / 2 )Si(CH2)2SCH2CH2CH2S(CH2)2Si(O 3 / 2 ] d2 ;

[0035] D 3 is

[0036] [(O 3 / 2 )Si(CH2)2SCH2CH2SCH2CH2CH2SCH2CH2SH] d1 [(O 3 / 2 )Si(CH2)2SCH2CH2S(CH2)2Si(O 3 / 2 ] d2 ;

[0037] D 4 is

[0038] [(O 3 / 2 )Si(CH2)2SCH2CH2SCH2CH2CH2SCH2CH2CH2SH] d1 [(O 3 / 2 )Si(CH2)2SCH2CH2S(CH2)2Si(O 3 / 2 ] d2 ;

[0039] D 5 is

[0040] [(O 3 / 2)Si(CH2)2SCH2CH2CH2SCH2CH2CH2SCH2CH2SH] d1 [(O 3 / 2)Si(CH2)2SCH2CH2CH2S(CH2)2Si(O 3 / 2 )] d2 ;

[0041] D 6 is

[0042] [(O 3 / 2 )Si(CH2)2SCH2CH2CH2SCH2CH2CH2SCH2CH2SH] d1 [(O 3 / 2 )Si(CH2)2SCH2CH2CH2S(CH2)2Si(O 3 / 2 )] d2 ;

[0043] E is

[0044] [(O 3 / 2 )Si(CH2)3SCH2CH2CH2NR 3 R 4 ];

[0045] F is

[0046] [(O 3 / 2 )Si(CH2) n SCH2CH2CH2SR] f1 [(O 3 / 2 )Si(CH2) n SCH2CH2CH2S(CH2) n Si(O 3 / 2 )] f2 ;

[0047] G is

[0048] [(O 3 / 2 )Si(CH2) n SCH2CH2SR] g1 [(O 3 / 2 )Si(CH2) n SCH2CH2S(CH2) n Si(O 3 / 2 )] g2 ;

[0049] H is

[0050] [(O 3 / 2 )Si(CH2) n SCH2CH2S(CH2)3NZR]

[0051] J is

[0052] [(O 3 / 2 )Si(CH2) n SCH2CH2CH2S(CH2)3NZR] ;

[0053] K is

[0054] [(O 3 / 2 )Si(CH2) n SCH2CH2S((CH2)3NZ(CH2)3SCH2CH2S) x R] k1 [(O 3 / 2 )Si(CH2) n SCH2CH2S-((CH2)3NZ(CH2)3SCH2CH2S) v (CH2) n Si(O 3 / 2 )] k2 [(O 3 / 2 )Si(CH2) n SCH2CH2S((CH2)3NZ(CH2)3-SCH2CH2S) i (CH2)3NZR] k3 ;

[0055] M is

[0056] [(O 3 / 2 )Si(CH2) n SCH2CH2CH2S((CH2)3NZ(CH2)3SCH2-CH2CH2S) x R] m1 [(O 3 / 2 )Si(CH2) n SCH2CH2CH2S((CH2)3NZ(CH2)3SCH2CH2CH2S) v (CH2) n -Si(O 3 / 2 )] m2 [(O 3 / 2 )Si(CH2) n SCH2CH2CH2S((CH2)3NZ(CH2)3SCH2CH2CH2S) i (CH2)3NZR] m3 ;

[0057] P is

[0058] [(O 3 / 2)Si(CH2) nSCH2CH2CH2S((CH2)2T(CH2)2SCH2CH2CH2S) x R p1 [(O 3 / 2 )Si(CH2) n SCH2CH2CH2S((CH2)2T(CH2)2SCH2CH2CH2S) v (CH2) n Si(O 3 / 2 )] p2 [(O 3 / 2 )Si-(CH2) n SCH2CH2CH2S((CH2)2T(CH2)2SCH2-CH2CH2S) i (CH2)2TR p3 ;

[0059] U is

[0060] [(O 3 / 2 )Si(CH2)3S(CH2)3NHC(=S)NH2; V is [O 3 / 2 Si(CH2) n S[(CH2) n1 S] n2 R 9 ; wherein Z is independently selected from hydrogen, C 1-22 -alkyl, C 2-22 -alkenyl, CONHR 5 , CSNHR 5 or COOR 5 ;

[0061] R Z is independently selected from hydrogen, C 1-22 -alkyl or C 2-22 -alkenyl; T is optionally substituted C 2-22 -alkyl or C 2-22 -cycloalkyl; R is selected from hydrogen, C 1-22 -alkyl, C 2-22 -alkenyl or acyl COR 2 ; R 1 is optionally selected and is selected from C 1-22 -alkyl, C 2-22 -alkenyl, C 2-22 -alkynyl, aryl, alkylamino, alkylpolyalkylamino or mercaptoalkyl; R 2 and R 5 are independently selected from hydrogen, C 1-22 -alkyl or C 2-22 -alkenyl; R 3 and R 4 or are independently selected from hydrogen, C1-22 - alkyl, alkylamino, alkylpolyamino or trialkylammonium group, or R 3 and R 4 are each C 3-12 - cycloalkyl or C 3-12 - cycloheteroalkyl; R 9 is CH2]3N + (L 1 )(CH3)2CH2CH2CH3, (CH2)3N + (L 1 )(CH3)2CH2CHCH2 and compounds of general formula III; n3 is an integer between 1 and 100; L 1 is an anion, including but not limited to halide, nitrate, sulfate, carbonate, phosphate, chromate, permanganate, borohydride, cyanoborohydride;

[0062]

[0063] n and n1 are each an integer of 2 or 3; n2 is an integer between 0 and 100; i, x and v are each an integer between 1 and 100; q is an integer from 1 to 3, z is an integer from 0 to 2, and q+z=3; a, a1-3, lb, lb1-3, 2b, 2b1-3, lc, lc1-2, 2c, 2c1-2, 3c, 3c1-2, 4c, 4c1-2, ld, ld1-2, 2d, 2d1-2, 3d, 3d1-2, 4d, 4d1-2, 5d, 5d1-2, 6d, 6d1-2, e, f, f12, g, g12, h, j, k, k13, m, ml-3, p, pl-3, u, ul-3, v, x, w and y are each an integer, and y:a+(1-2)b+(1-4)c+(1-6)d+e+f+g+h+j+k+m+v+w+x is 0.01 to 10000, y:a+(1-2)b+(1-4)c+(1-6)d+e+f+g+v+w+x is 0.01 to 10000, y:f+g+h+j+k+m+v+w+x is 0.01 to 10000, y:e+f+g+w+x is 0.01 to 10000, y:f+g+h+j+p+u+v+w+x is 0.01 to 10000; the following ratios a1:a3, a1:a2+a3, lb2:lb1+lb3, 2b2:2b1+2b3, lc1:lc2, 2c1:2c2, 3c1:3c2, 4c1:4c2, ld1:ld2, 2d1:2d2, 3d1:3d2, 4d1:4d2, 5d1:5d2, 6d1:6d2, f1:f2, g1:g2, k1:k3, k1:k2+k3, ml:m3, ml:m2+m3, pl:p3, pl:p2+p3 are each different and are between 0.01 and 100; in formula I, component Y is always present, at least one of components K, M, P, V is always present, and the remaining components are present or absent;

[0064] Further, in step (1), one of the methods for preparing the functionalized silica gel material is:

[0065] The solution of 1,3-dimercaptopropane and diallylamine is heated to 100-140°C and then heated for 2-5 h, adding di-t-butyl peroxide (5-15 mL) dropwise every 10-20 min. Vinyltrimethoxysilane is added and the solution is heated at 110-130°C for 2-5 h, adding di-t-butyl peroxide (5-15 mL) dropwise every 10-20 min, then cooled to 50-70°C and added to a stirred mixture of silica gel (6.0 kg, 60-200 μm) and toluene (12-16 L). In addition, N-methyl, N 13-(3-(2-triethylsilyl ethyl sulfanyl)propylthio)propylthiourea and toluene (70-130 mL). After stirring and refluxing the mixture for 0.5-2 h, N-3-(3-trimethoxysilylpropylthio)propylthiourea (CH3O)3SiC3H6SC3H6NHC(=S)NH2(prepared from allylthiourea and trimethoxysilylpropane trisulfide at 110-140 °C for 1-4 h) is added and the mixture is stirred and refluxed for another 3-6 h. After cooling, the solid is filtered, washed thoroughly with methanol, and dried to obtain a composition of Formula I, wherein Y, F, J, M and U are all present, n is 2, Z in J is C=SNHCH3, and Z in M is hydrogen.

[0066] Further, the molar ratio of 1,3-dimercaptopropane to diallylamine is 1-2:1. The molar ratio of vinyltrimethoxysilane to diallylamine is 0.5-1:1. The molar ratio of 3-(3-(2-triethylsilyl ethyl sulfanyl)propylthio)propylthiourea to diallylamine is 0.1-0.5:1. The molar ratio of N-3-(3-trimethoxysilylpropylthio)propylthiourea (CH3O)3SiC3H6SC3H6NHC(=S)NH2to diallylamine is 0.01-0.05:1. 1 3-(3-(2-triethylsilyl ethyl sulfanyl)propylthio)propylthiourea and toluene (70-130 mL). After stirring and refluxing the mixture for 0.5-2 h, N-3-(3-trimethoxysilylpropylthio)propylthiourea (CH3O)3SiC3H6SC3H6NHC(=S)NH2(prepared from allylthiourea and trimethoxysilylpropane trisulfide at 110-140 °C for 1-4 h) is added and the mixture is stirred and refluxed for another 3-6 h. After cooling, the solid is filtered, washed thoroughly with methanol, and dried to obtain a composition of Formula I, wherein Y, F, J, M and U are all present, n is 2, Z in J is C=SNHCH3, and Z in M is hydrogen.

[0067] Further, in step (1), the mass ratio of the functionalized silica gel material to rhodium in the rhodium-containing solution is 100:1-2:1, preferably 80:1-10:1, in terms of elements.

[0068] Further, in step (1), the adsorption is performed at 30-80 °C for 2-10 hours.

[0069] Further, in step (1), the washing can be performed by using conventional methods in the art, such as using ethanol.

[0070] Further, the method for preparing graphene oxide in step (2) specifically comprises:

[0071] Concentrated sulfuric acid is placed in a beaker and is placed in an ice water bath, graphite powder is added and is ultrasonically treated, the ultrasonics is turned off, potassium permanganate is added, the first stirring is performed at the ice water bath for 0.5-5 hours, then the temperature is increased to 30-60 °C and the second stirring is performed for 0.5-5 hours, then the temperature is further increased to 80-100 °C and the third stirring is started, water is added and the reaction is continued for 0.5-5 hours; the obtained material is cooled, hydrogen peroxide solution is added until the solution becomes bright yellow, is filtered, washed, the obtained sample is centrifuged, dried, and ground to obtain graphene oxide.

[0072] Further, in the process for preparing graphene oxide, the mass concentration of the concentrated sulfuric acid is 80%-98%.

[0073] Further, in the process of preparing graphene oxide, the mass-volume ratio of the graphite powder to concentrated sulfuric acid is 1:10-1:100 (g / mL).

[0074] Further, in the process of preparing graphene oxide, the ultrasonic treatment is performed for 1-4 hours at a frequency of 15-30 kHz.

[0075] Further, in the process of preparing graphene oxide, the mass ratio of the graphite powder to potassium permanganate is 1:1-1:10.

[0076] Further, in the process of preparing graphene oxide, the first stirring is performed at a rate of 300-700 r / min, the second stirring is performed at a rate of 300-700 r / min, and the third stirring is performed at a rate of 200-500 r / min. Preferably, the rate of the third stirring is lower than the rates of the first and second stirrings.

[0077] Further, in the process of preparing graphene oxide, after the third stirring, the water added is preferably deionized water, and the volume ratio of the water to concentrated sulfuric acid is 1:1-5:1.

[0078] Further, in the process of preparing graphene oxide, the mass concentration of the hydrogen peroxide solution is 25-30 wt%.

[0079] Further, in the process of preparing graphene oxide, the washing can be performed by using a conventional washing method in the art, for example, the graphene oxide can be first washed with a dilute acid solution (e.g., dilute hydrochloric acid, dilute nitric acid, etc.) until no sulfate is present, and then washed with deionized water.

[0080] Further, in the process of preparing graphene oxide, the drying is performed at 60-120 °C for 4-12 hours.

[0081] Further, in the process of preparing graphene oxide, the grinding can be performed by using a mortar to grind the graphene oxide into powder.

[0082] Further, in step (3), the solvent is at least one of tetrahydrofuran, cyclohexane, anhydrous ethanol, toluene, and petroleum ether. The vulcanizing agent is at least one of dicumyl peroxide (DCP), N,N'-m-phenylene bismaleimide (PDM), and sulfur. The emulsifier is at least one of polyethylene glycol octylphenyl ether (triton X-100), alkylphenol polyoxyethylene ether, and fatty acid polyoxyethylene ester.

[0083] Further, in step (3), the mass-volume ratio of the rhodium-loaded functionalized silica gel material to the solvent is 1:1-1:10 (g / mL). The mass ratio of the sulfurizing agent to the rhodium-loaded functionalized silica gel material is 1:40-1:100. The mass-volume ratio of the emulsifying agent to the rhodium-loaded functionalized silica gel material is 1:1-1:5 (g / mL).

[0084] Further, in step (3), the mass-volume ratio of the graphene oxide to water is 1:100-1:500 (g / mL).

[0085] Further, in step (3), the ultrasonic dispersion condition is that the frequency is 15-30 kHz and the time is 0.5 h-4 h.

[0086] Further, in step (3), the mass ratio of the graphene oxide to the rhodium-loaded functionalized silica gel material is 1:10-1:50.

[0087] Further, in step (3), the first stirring condition is that the rotation speed is 700 r / min-2000 r / min and the time is 10 min-300 min.

[0088] Further, in step (3), the second stirring condition is that the rotation speed is 700 r / min-2000 r / min and the time is 10 min-300 min.

[0089] Further, in step (3), the shearing condition is that the rotation speed is 7000 r / min-20000 r / min and the pressure is 0.6-0.8 MPa.

[0090] Further, in step (3), the reducing agent is at least one of pyridine and ascorbic acid.

[0091] Further, in step (3), after adding the reducing agent, the heating condition is that heating at 60-150℃ for 2-8 hours.

[0092] Further, in step (3), the washing can be deionized water washing. The drying condition is vacuum drying at 80-120℃ for 6 h-12 h.

[0093] Further, in step (3), the sulfurization condition is that the sulfurization temperature is 140-250℃ and the sulfurization time is 10-60 minutes.

[0094] The second aspect of the present application provides a rhodium-based catalyst prepared by the above method.

[0095] Further, in the rhodium-based catalyst, the mass content of rhodium in terms of elements is 2wt%-15wt%.

[0096] The third aspect of the present application provides a use of the rhodium-based catalyst prepared by the above method in a hydroformylation reaction of hydrocarbons.

[0097] Further, the reaction is specifically: under the action of the rhodium-based catalyst, C2-C14 olefins are contacted with synthesis gas at 60-140℃. In the reaction system, the amount of the rhodium-based catalyst is 100-1500 ppm in terms of metallic rhodium, in terms of mass fraction. The H2 / CO molar ratio in the synthesis gas is 3:1-1:3. The preferred molar ratio of the synthesis gas to the olefins is 1-10:1.

[0098] Compared with the prior art, the present application has the following advantages:

[0099] 1. The rhodium-based catalyst prepared by the preparation method of the present application, compared with the commonly used rhodium catalyst, can effectively improve the conversion rate and the normal / iso ratio in the olefin hydroformylation reaction, and the rhodium-based catalyst of the present application is less likely to dissolve in the reaction, reducing the loss of rhodium.

[0100] 2. The preparation method of the present application can also realize efficient recovery of rhodium in low-concentration rhodium-containing waste liquid, reducing production cost. DETAILED DESCRIPTION

[0101] The technical solutions of the present application will be described in detail below in combination with examples, but the present application is not limited to the following examples. Based on the examples in the present application, all other examples obtained by those skilled in the art without creative labor are within the scope of protection of the present application.

[0102] Example 1

[0103] 10 g of functionalized silica gel material (functionalized silica gel material prepared according to the method of Example 10 in CN110191911B) was taken and added to 1.5 L of waste liquid containing 380 ppm of rhodium, the rhodium was derived from the rhodium iodide catalyst used; the mixture was stirred at 80℃ for 8 h after adsorption and then filtered, washed with 1000 mL of ethanol to obtain rhodium-loaded functionalized silica gel material Rh / Si-gel.

[0104] Take 70 mL of 98% mass fraction sulfuric acid in a beaker, and place it in an ice water bath, add 5 g of graphite powder ultrasonic 2.5 hours, ultrasonic frequency is 20 kHz, turn off the ultrasonic, add 7 g of potassium permanganate, stirring at 600 r / min for 3 hours, while keeping the temperature in ice bath conditions. Then control the temperature at 60 ℃ for 2 hours at 600 r / min stirring rate, continue to heat to 90 ℃ start low speed stirring at 400 r / min, drop 150 mL of deionized water, continue to react for 2 hours. The resulting solution is placed at room temperature drop 30 wt% hydrogen peroxide solution, until the solution becomes bright yellow, hot filtration, washed with 10 wt% dilute nitric acid until no SO4 2- Then washed with deionized water, the resulting sample is centrifuged, dried at 100 ℃ for 12 h, grinding to get graphene oxide GO.

[0105] Take 10 g of Rhodium loaded functionalized silica gel material Rh / Si-gel in a beaker, add 50 mL of toluene stirring to dissolve, add 0.2 g of vulcanizing agent dicumyl peroxide (DCP) and 5 mL of emulsifier Triton X-100, stirring at 1000 r / min for 30 min to mix evenly, get the mixture; 400 mg of graphene oxide GO is added to 100 mL of water and ultrasonic dispersed, ultrasonic frequency is 20 kHz, ultrasonic for 1 hour, then it is added dropwise to the above mixture, continue to stir at 1000 r / min for 20 min, get the graphene oxide and Rhodium loaded functionalized material GO / RS mixed solution; using a high speed shearing machine under the conditions of pressure 0.6 MPa, speed 10000 r / min, shearing the GO / RS mixed solution for 5 min, then continue to stir at 0.6 MPa pressure and 10000 r / min speed in a magnetic stirrer for 30 min, get the uniformly dispersed GO / RS emulsion.

[0106] Take 20 mL of GO / RS emulsion in a sample bottle, add an appropriate amount of reducing agent ascorbic acid, heat at 90 ℃ for 4 h, in the process of heating, the graphene oxide is reduced to form a three-dimensional gel, at the same time, the molecular chain of Rh / Si-gel is doped in the gel, get the three-dimensional doped Rh catalyst graphene oxide / silica RGO / RS gel. The RGO / RS gel is repeatedly washed and soaked in water to remove excess reducing agent, then placed in a vacuum drying oven at 110 ℃ for 6 h until the total weight is constant, then use a flat vulcanizer at 170 ℃ for 20 min, get the composite material - Rh-based catalyst (the mass content of Rh is 2.5 wt%).

[0107] Example 2

[0108] Take 10 g of functionalized silica gel material (functionalized silica gel material prepared according to the description of CN110191911B, Example 9) and add it to 1 L of waste liquid containing 1000 ppm of rhodium, which comes from the acetylacetone rhodium carbonyl catalyst used; stir the mixture at 60°C for 7 h after adsorption, then filter and wash with 1000 mL of ethanol to obtain the rhodium-loaded functionalized silica gel material Rh / Si-gel.

[0109] Measure 60 mL of 98% mass fraction sulfuric acid in a beaker and place it in an ice water bath, add 3 g of graphite powder and ultrasonic for 2.5 hours, the ultrasonic frequency is 20 kHz, turn off the ultrasonic, add 10 g of potassium permanganate, stir at a speed of 600 r / min for 3 hours, and keep the temperature in ice bath condition. Then control the temperature at 60°C and continue to stir at a speed of 600 r / min for 4 hours, continue to heat to 90°C and start to stir at a low speed of 400 r / min, add 150 mL of deionized water dropwise, continue to react for 2 hours. Place the resulting solution at room temperature and add 30 wt% hydrogen peroxide solution dropwise until the solution turns bright yellow, filter hot and rinse with dilute nitric acid until SO4 2- Then rinse with deionized water, centrifuge the resulting sample, dry at 100°C for 12 h, and grind to obtain graphene oxide GO.

[0110] Take 10 g of rhodium-loaded functionalized silica gel material Rh / Si-gel and place it in a beaker, add 60 mL of cyclohexane and stir to dissolve, then add 0.2 g of vulcanizing agent N, N'-m-phenylene bismaleimide (PDM) and 5 mL of emulsifier Triton X-100, stir at a speed of 1000 r / min for 20 min until the mixture is uniform, to obtain a mixture; ultrasonic dispersion of 400 mg of graphene oxide GO in 100 mL of water, ultrasonic frequency is 20 kHz, ultrasonic for 1 hour; add it dropwise to the above mixture, continue to stir at a speed of 1000 r / min for 20 min to obtain a GO / RS mixed solution; high-speed shearing machine under the conditions of pressure 0.7 Mpa and speed 10000 r / min, shear the GO / RS mixed solution for 15 min, then continue to stir in a magnetic stirrer at a pressure of 0.6 Mpa and a speed of 10000 r / min for 40 min, to obtain a uniformly dispersed GO / RS emulsion.

[0111] Take 20 mL of GO / RS emulsion into a sample bottle, add an appropriate amount of reducing agent pyridine, heat at 90°C for 4h, in the process of heating, the graphene oxide is reduced to form a three-dimensional gel, at the same time, the molecular chains of Rh / Si-gel are doped into the gel, and a three-dimensional RGO / RS gel is obtained. The RGO / RS gel is repeatedly washed and soaked in water to remove excess reducing agent, and then placed in a vacuum drying oven at 110°C for 6h until the total weight is constant, and then a flat plate vulcanizer is used at 200°C for 15min to obtain a composite material, i.e. a rhodium-based catalyst (the mass content of rhodium is 5wt%).

[0112] Example 3

[0113] Take 10g of functionalized silica gel material (functionalized silica gel material prepared according to the method of Example 3 in CN110191911B), and add it to 2L of waste liquid containing 390ppm of rhodium, which comes from the used rhodium iodide catalyst; after stirring at 80°C for 8h, the mixture is filtered and washed with 1000mL of ethanol to obtain a rhodium-loaded functionalized silica gel material Rh / Si-gel.

[0114] Measure 65mL of 98% mass fraction sulfuric acid in a beaker, and place it in an ice water bath, add 4g of graphite powder and ultrasonic for 2.5 hours, the ultrasonic frequency is 20kHz, turn off the ultrasonic, add 7g of potassium permanganate, and stir at a rate of 650r / min for 3 hours, while keeping the temperature in ice bath condition. Then control the temperature at 60°C for 2 hours at a rate of 650r / min, continue to heat to 90°C, start to stir at a low speed of 400r / min, add 150mL of deionized water dropwise, continue to react for 3 hours. Place the obtained solution at room temperature, add 30wt% hydrogen peroxide solution dropwise until the solution turns bright yellow, filter while hot, rinse with 10wt% dilute nitric acid until SO4 2- Then wash with deionized water, centrifuge the obtained sample, dry at 100°C for 12h, and grind to obtain graphene oxide GO.

[0115] Take 10 g of functionalized silica gel material loaded with rhodium Rh / Si-gel and place it in a beaker. Add 55 mL of toluene and stir to dissolve. Then add 0.3 g of vulcanizing agent dicumyl peroxide (DCP) and 6 mL of emulsifier Triton X-100. Stir at a speed of 1000 r / min for 30 min until the mixture is uniform. Then take 400 mg of graphene oxide GO and disperse it in 100 mL of water using ultrasonic waves at a frequency of 20 kHz for 1.5 h. Then add the dispersion to the above mixture and continue stirring at a speed of 1000 r / min for 20 min to obtain a GO / RS mixed solution of functionalized material loaded with rhodium. Use a high-speed shearing machine to shear the GO / RS mixed solution at a pressure of 0.6 Mpa and a speed of 10000 r / min for 5 min. Then continue to stir the solution at a pressure of 0.6 Mpa and a speed of 10000 r / min for 30 min using a magnetic stirrer to obtain a uniformly dispersed GO / RS emulsion.

[0116] Take 20 mL of the GO / RS emulsion and place it in a sample bottle. Add an appropriate amount of reducing agent ascorbic acid and heat at 90°C for 5 h. In the process of heating, the graphene oxide is reduced to form a three-dimensional gel, and the molecular chains of Rh / Si-gel are doped into the gel. Thus, a three-dimensional doped rhodium catalyst RGO / RS gel of graphene oxide / silica is obtained. Wash and soak the RGO / RS gel in water repeatedly to remove excess reducing agent. Then place the gel in a vacuum drying oven at 100°C for 6 h until the total weight remains unchanged. Then use a flat plate vulcanizer to vulcanize at 180°C for 20 min to obtain a composite material, a rhodium-based catalyst (the mass content of rhodium is 4 wt%).

[0117] Example 4

[0118] Take 10 g of functionalized silica gel material (prepared according to the functionalized silica gel material in Example 21 of CN110191911B) and add it to 1 L of waste liquid containing 850 ppm of rhodium. The rhodium comes from the acetylacetone rhodium carbonyl catalyst used. Stir the mixture at 70°C for 7 h to adsorb, then filter and wash with 1000 mL of ethanol to obtain a functionalized silica gel material loaded with rhodium Rh / Si-gel.

[0119] Take 80 mL of 98% mass fraction sulfuric acid in a beaker, and place it in an ice water bath, add 4 g of graphite powder ultrasonic 2.5 hours, ultrasonic frequency is 20 kHz, turn off the ultrasonic, add 8 g of potassium permanganate, stirring at 700 r / min for 3 hours, while keeping the temperature in ice bath conditions. Then control the temperature at 60 ℃ to continue stirring at 700 r / min for 4 hours, continue to heat to 90 ℃ to start low speed stirring at 400 r / min, drop 150 mL of deionized water, continue to react for 2 hours. The resulting solution is placed at room temperature drop 30 wt% hydrogen peroxide solution until the solution becomes bright yellow, hot filtration, rinse with dilute nitric acid until no SO4 2- Then rinse with deionized water, centrifuge the resulting sample, dry at 100 ℃ for 12 h, grind to get graphene oxide GO.

[0120] Take 10 g of functionalized silica gel material loaded with rhodium Rh / Si-gel in a beaker, add 70 mL of cyclohexane, stir to dissolve, then add 0.4 g of vulcanizing agent N, N'-m-phenylene bismaleimide (PDM) and 6 mL of emulsifier Triton X-100, stir at 1000 r / min for 25 min until mixed evenly, to get the mixture; ultrasonic dispersion of 400 mg of graphene oxide GO with 100 mL of water, ultrasonic frequency is 20 kHz, ultrasonic 1.5 hours; drop it into the above mixture, continue to stir at 1000 r / min for 30 min, to get GO / RS mixed solution; high speed shear machine under the conditions of pressure 0.7 Mpa, speed 10000 r / min, shear GO / RS mixed solution for 20 min, then continue to stir at 0.7 Mpa pressure and 10000 r / min speed in a magnetic stirrer for 50 min, to get uniformly dispersed GO / RS emulsion.

[0121] Take 20 mL of GO / RS emulsion in a sample bottle, add an appropriate amount of reducing agent pyridine, heat at 85 ℃ for 4 h, in the process of heating, the graphene oxide is reduced to form a three-dimensional gel, at the same time, the molecular chain of Rh / Si-gel is doped in the gel, to get three-dimensional RGO / RS gel. The RGO / RS gel is repeatedly washed and soaked in water to remove excess reducing agent, then placed in a vacuum drying oven at 110 ℃ for 6 h until the total weight is constant, then use a flat vulcanizer at 190 ℃ for 20 min, to get the composite material, rhodium-based catalyst (the mass content of rhodium is 4.3 wt%).

[0122] Comparative Example 1

[0123] Compared with Example 1, the only difference is that 10 g of functionalized silica gel material is replaced by conventional commercial fluorosilicone rubber. The others are the same as Example 1. Finally, a rhodium-based catalyst is prepared.

[0124] Example 5

[0125] Propylene, synthesis gas, triphenylphosphine and rhodium-based catalyst obtained in Example 1 (solvent is n-hexane, the amount of rhodium-based catalyst in the solution is 300 ppm in terms of metallic rhodium) were put into a high-pressure reactor, wherein, at T = 90°C, r = 300 r / min, H2 / CO molar ratio = 1:1, the molar ratio of the feeding of synthesis gas to propylene was kept at 2:1, after 4 hours of reaction, the reaction was stopped and cooled, the reaction product was taken out after it reached room temperature, and it was found by chromatographic detection that the conversion rate of propylene reached 97%, the yield of product n-butyraldehyde was 94.6%, and the n-iso ratio was 40:1.

[0126] Example 6

[0127] Compared with Example 5, the only difference is that the catalyst used is the rhodium-based catalyst obtained in Example 2, and it was found by chromatographic detection that the conversion rate of propylene reached 98%, the yield of product n-butyraldehyde was 95.5%, and the n-iso ratio was 38:1.

[0128] Example 7

[0129] Isobutylene, synthesis gas, triphenylphosphine and rhodium-based catalyst obtained in Example 3 (solvent is n-hexane, the amount of rhodium-based catalyst in the solution is 300 ppm in terms of metallic rhodium) were put into a high-pressure reactor, wherein, at T = 90°C, r = 300 r / min, H2 / CO molar ratio = 1:1, the molar ratio of the feeding of synthesis gas to isobutylene was kept at 2:1, after 4 hours of reaction, the reaction was stopped and cooled, the reaction product was taken out after it reached room temperature, and it was found by chromatographic detection that the conversion rate of isobutylene reached 98.4%, the yield of product isoamyl aldehyde was 98%.

[0130] Example 8

[0131] Compared with Example 7, the only difference is that the catalyst used is the rhodium-based catalyst obtained in Example 4, and it was found by chromatographic detection that the conversion rate of isobutylene reached 97.8%, the yield of product isoamyl aldehyde was 97.5%.

[0132] Comparative Example 2

[0133] Propylene, synthesis gas, triphenylphosphine and rhodium-based catalyst obtained in Example 1 (solvent is n-hexane, the amount of rhodium-based catalyst in the solution is 300 ppm in terms of metallic rhodium) were put into a high-pressure reactor, wherein, at T = 90°C, r = 300 r / min, H2 / CO molar ratio = 1:1, the molar ratio of the feeding of synthesis gas to propylene was kept at 2:1, after 4 hours of reaction, the reaction was stopped and cooled, the reaction product was taken out after it reached room temperature, and it was found by chromatographic detection that the conversion rate of propylene reached 97%, the yield of product n-butyraldehyde was 94.6%, and the n-iso ratio was 40:1.

[0134] Comparative Example 3

[0135] Isobutene, synthesis gas, triphenylphosphine and rhodium piperidine (solvent is n-hexane, the amount of rhodium compound in the solution is 300 ppm in terms of metallic rhodium) were put into a high-pressure reactor, wherein, at T = 90°C, r = 300 r / min, H2 / CO molar ratio = 1:1, the molar ratio of synthesis gas to isobutene was kept at 2:1, after 4 hours of reaction, the reaction was stopped and cooled, and after the reaction product was taken out at room temperature, it was found by chromatographic detection that the conversion rate of isobutene reached 74.8%, and the yield of isovaleraldehyde was 73.2%.

[0136] Comparative Example 4

[0137] Propylene, synthesis gas, triphenylphosphine and rhodium-based catalyst prepared in Comparative Example 1 (solvent is n-hexane, the amount of rhodium-based catalyst in the solution is 300 ppm in terms of metallic rhodium) were put into a high-pressure reactor, wherein, at T = 90°C, r = 300 r / min, H2 / CO molar ratio = 1:1, the molar ratio of synthesis gas to propylene was kept at 2:1, after 4 hours of reaction, the reaction was stopped and cooled, and after the reaction product was taken out at room temperature, it was found by chromatographic detection that the conversion rate of propylene reached 77.9%, and the yield of n-butyraldehyde was 75.1%, and the n-isomer ratio was 27:1.

[0138] Example 9

[0139] The solution after reaction in Example 5 and Example 7 was taken for atomic absorption rhodium element detection, and the rhodium content in the reaction solution in Example 5 was 23 ppm, and the rhodium content in the reaction solution in Example 7 was 19 ppm.

[0140] Comparative Example 5

[0141] The solution after reaction in Comparative Example 2, Comparative Example 3 and Comparative Example 4 was taken for atomic absorption rhodium element detection, and the rhodium content in the reaction solution in Comparative Example 2 was 72 ppm, the rhodium content in the reaction solution in Comparative Example 3 was 70 ppm, and the rhodium content in the reaction solution in Comparative Example 4 was 75 ppm.

[0142] The above detailed the specific embodiments of the present application, but the present application is not limited thereto. Within the technical concept of the present application, various simple modifications can be made to the technical solutions of the present application, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be considered as disclosed by the present application, and all fall within the protection scope of the present application.

Claims

1. A method for preparing a rhodium-based catalyst, characterized in that: Includes the following steps: (1) The functionalized silica material was placed in a rhodium-containing solution and adsorbed under stirring. Then it was filtered and washed to obtain the rhodium-loaded functionalized silica material. (2) Preparation of graphene oxide; (3) Add solvent, vulcanizing agent and emulsifier to the rhodium-loaded functionalized silicone material obtained in step (1), stir for the first time to obtain a mixture; mix the graphene oxide obtained in step (2) with water and disperse it ultrasonically, add it to the mixture, stir for the second time, and then shear to obtain a mixed emulsion; then add a reducing agent, heat, wash, dry and vulcanize to obtain a rhodium-based catalyst. The vulcanizing agent is at least one of dicumyl peroxide, N,N'-m-phenylenebismaleimide, and sulfur; the emulsifier is at least one of polyethylene glycol octylphenyl ether, alkylphenol polyoxyethylene ether, and fatty acid polyoxyethylene ester. The reducing agent is at least one of pyridine and ascorbic acid; After adding the reducing agent, the heating conditions are: heating at 60-150℃ for 2-8 hours; The vulcanization conditions are: vulcanization temperature of 140-250℃ and vulcanization time of 10-60 minutes.

2. The preparation method according to claim 1, characterized in that: In step (1), the rhodium-containing solution is a rhodium-containing waste liquid; in the rhodium-containing solution, the rhodium source is at least one of triphenylphosphine acetylacetone carbonyl rhodium, rhodium trichloride, rhodium iodide, and acetylacetone carbonyl rhodium. And / or, the mass concentration of rhodium in the rhodium-containing solution is 300ppm-2000ppm (elemental).

3. The preparation method according to claim 1, characterized in that: In step (1), the mass ratio of the functionalized silicone material to the rhodium in the rhodium-containing solution is 100:1-2:1 (by element).

4. The preparation method according to claim 3, characterized in that: In step (1), the mass ratio of the functionalized silicone material to the rhodium in the rhodium-containing solution is 80:1-10:

1.

5. The preparation method according to claim 1, characterized in that: Step (2) of the method for preparing graphene oxide specifically includes: Concentrated sulfuric acid was placed in a beaker and then placed in an ice-water bath. Graphite powder was added and ultrasonically treated. The ultrasonic treatment was then turned off, and potassium permanganate was added. The mixture was stirred for 0.5-5 hours in the ice-water bath. Then, the temperature was raised to 30-60℃ and stirred for 0.5-5 hours. The temperature was then raised to 80-100℃ and stirred for 0.5-5 hours. Water was added and the reaction was continued for 0.5-5 hours. After cooling the resulting material, hydrogen peroxide solution was added until the solution turned bright yellow. The mixture was filtered, washed, and the resulting sample was centrifuged, dried, and ground to obtain graphene oxide.

6. The preparation method according to claim 1, characterized in that: In step (3), the solvent is at least one of tetrahydrofuran, cyclohexane, anhydrous ethanol, toluene, and petroleum ether.

7. The preparation method according to claim 1, characterized in that: In step (3), the mass-to-volume ratio of the rhodium-loaded functionalized silicone material to the solvent is 1:1-1:10 (g / mL); the mass ratio of the vulcanizing agent to the rhodium-loaded functionalized silicone material is 1:40-1:100; the mass-to-volume ratio of the emulsifier to the rhodium-loaded functionalized silicone material is 1:1-1:5 (g / mL); the mass-to-volume ratio of the graphene oxide to water is 1:100-1:500 (g / mL); and the mass ratio of the graphene oxide to the rhodium-loaded functionalized silicone material is 1:10-1:

50.

8. The preparation method according to claim 1, characterized in that: In step (3), the conditions for the first stirring are: a rotation speed of 700 r / min-2000 r / min and a time of 10 min-300 min; And / or, the conditions for the second stirring are: a rotation speed of 700 r / min-2000 r / min and a time of 10 min-300 min; And / or, the shearing conditions are: rotation speed of 7000 r / min-20000 r / min and pressure of 0.6-0.8 MPa.

9. A rhodium-based catalyst prepared by the method according to any one of claims 1-8.

10. The application of the rhodium-based catalyst prepared by any one of claims 1-8 in the hydroformylation reaction of hydrocarbons.

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