CN113750994B - Catalyst for producing 3,3',4,4' -biphenyl tetracarboxylic acid and preparation method thereof - Google Patents
Catalyst for producing 3,3',4,4' -biphenyl tetracarboxylic acid and preparation method thereof Download PDFInfo
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- CN113750994B CN113750994B CN202111225694.5A CN202111225694A CN113750994B CN 113750994 B CN113750994 B CN 113750994B CN 202111225694 A CN202111225694 A CN 202111225694A CN 113750994 B CN113750994 B CN 113750994B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 102
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- LFBALUPVVFCEPA-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C(C(O)=O)=C1 LFBALUPVVFCEPA-UHFFFAOYSA-N 0.000 title claims description 19
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 118
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 73
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 63
- 239000002131 composite material Substances 0.000 claims abstract description 35
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000000292 calcium oxide Substances 0.000 claims description 56
- 239000002243 precursor Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical group Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims description 22
- 239000000395 magnesium oxide Substances 0.000 claims description 22
- 239000002002 slurry Substances 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000011268 mixed slurry Substances 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 14
- ZNBNBTIDJSKEAM-UHFFFAOYSA-N 4-[7-hydroxy-2-[5-[5-[6-hydroxy-6-(hydroxymethyl)-3,5-dimethyloxan-2-yl]-3-methyloxolan-2-yl]-5-methyloxolan-2-yl]-2,8-dimethyl-1,10-dioxaspiro[4.5]decan-9-yl]-2-methyl-3-propanoyloxypentanoic acid Chemical compound C1C(O)C(C)C(C(C)C(OC(=O)CC)C(C)C(O)=O)OC11OC(C)(C2OC(C)(CC2)C2C(CC(O2)C2C(CC(C)C(O)(CO)O2)C)C)CC1 ZNBNBTIDJSKEAM-UHFFFAOYSA-N 0.000 claims description 13
- 229910000378 hydroxylammonium sulfate Inorganic materials 0.000 claims description 13
- 230000001105 regulatory effect Effects 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 11
- 125000001477 organic nitrogen group Chemical group 0.000 claims description 11
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 10
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 7
- 239000003638 chemical reducing agent Substances 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- 239000002023 wood Substances 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 5
- 159000000007 calcium salts Chemical class 0.000 claims description 5
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 5
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 5
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 5
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical group [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- 159000000003 magnesium salts Chemical class 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical group [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 238000006722 reduction reaction Methods 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 11
- 239000002184 metal Substances 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 9
- 229910000510 noble metal Inorganic materials 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 abstract description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 50
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 37
- 239000000243 solution Substances 0.000 description 34
- 239000007864 aqueous solution Substances 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 15
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Inorganic materials [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 8
- -1 optical filters Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000004642 Polyimide Substances 0.000 description 5
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 5
- 229920001721 polyimide Polymers 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 3
- 239000011218 binary composite Substances 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005695 dehalogenation reaction Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- FUSNOPLQVRUIIM-UHFFFAOYSA-N 4-amino-2-(4,4-dimethyl-2-oxoimidazolidin-1-yl)-n-[3-(trifluoromethyl)phenyl]pyrimidine-5-carboxamide Chemical compound O=C1NC(C)(C)CN1C(N=C1N)=NC=C1C(=O)NC1=CC=CC(C(F)(F)F)=C1 FUSNOPLQVRUIIM-UHFFFAOYSA-N 0.000 description 1
- DVIPPHSQIBKWSA-UHFFFAOYSA-N 4-chlorophthalic acid Chemical compound OC(=O)C1=CC=C(Cl)C=C1C(O)=O DVIPPHSQIBKWSA-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000012696 Pd precursors Substances 0.000 description 1
- 239000004280 Sodium formate Substances 0.000 description 1
- BPKGOZPBGXJDEP-UHFFFAOYSA-N [C].[Zn] Chemical compound [C].[Zn] BPKGOZPBGXJDEP-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- 239000012493 hydrazine sulfate Substances 0.000 description 1
- 229910000377 hydrazine sulfate Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- BSIDXUHWUKTRQL-UHFFFAOYSA-N nickel palladium Chemical compound [Ni].[Pd] BSIDXUHWUKTRQL-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- RCZJVHXVCSKDKB-UHFFFAOYSA-N tert-butyl 2-[[1-(2-amino-1,3-thiazol-4-yl)-2-(1,3-benzothiazol-2-ylsulfanyl)-2-oxoethylidene]amino]oxy-2-methylpropanoate Chemical compound N=1C2=CC=CC=C2SC=1SC(=O)C(=NOC(C)(C)C(=O)OC(C)(C)C)C1=CSC(N)=N1 RCZJVHXVCSKDKB-UHFFFAOYSA-N 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/58—Platinum group metals with alkali- or alkaline earth metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/353—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by isomerisation; by change of size of the carbon skeleton
Abstract
The invention discloses a catalyst for producing 3,3', 4' -biphenyl tetracarboxylic acid, which comprises a carrier and active component palladium loaded on the carrier, wherein the content of the palladium in the catalyst is 3-5% by weight percent, and the rest is the carrier; wherein the carrier is an MgO-CaO/C composite carrier composed of MgO, caO and active carbon, and the weight ratio of the MgO to the CaO is 100 percent, the content of MgO in the carrier is 2-5wt%, the content of CaO is 1-5wt%, and the balance is active carbon; meanwhile, the invention also discloses a preparation method of the catalyst. The acting force between the noble metal palladium and the carrier is improved by preparing the composite carrier MgO-CaO/C, the high dispersion of metal components is ensured, the metal is not easy to run off in the use process, and the catalyst has high reaction activity.
Description
Technical Field
The invention belongs to the technical field of noble metal catalyst preparation, and particularly relates to a catalyst for producing 3,3',4,4' -biphenyl tetracarboxylic acid and a preparation method thereof.
Background
The 3,3', 4' -biphenyl tetracarboxylic dianhydride is obtained by dehydration cyclization of 3,3', 4' -biphenyl tetracarboxylic dianhydride (BPTA). 3,3', 4' -biphenyltetracarboxylic dianhydride (BPDA) is an important polymer, a precursor of polyimide, which can be polymerized with polyfunctional amines to form polyimide. Because of the rigid structure of the BPDA, polyimide synthesized by taking the polyimide as a raw material is super heat-resistant resin with highest heat-resistant temperature so far, has excellent hydrolysis resistance, mechanical property and flexibility, can be used for manufacturing heat-resistant photosensitive resin, optical filters, liquid crystal displays, cross-linked adhesives of conductors and semiconductors, and can also be used for protecting materials used in lasers, lithium batteries and space. BPDA is also important as an important monomer for a high-performance wholly aromatic polyimide. In recent years, the synthesis method of 3,3',4,4' -biphenyl tetracarboxylic dianhydride is attracting attention of general technological staff and is continuously explored, and aims to reduce the cost of raw materials, shorten the synthetic process route and the like. The literature on the synthesis of 3,3', 4' -biphenyltetracarboxylic acid reports a lot, and the most widely used dehalogenation coupling method at present is that the catalyst for synthesizing BPDA by the dehalogenation coupling method mainly comprises two types of Pd catalyst and triarylphosphine ligand compound. Pd catalyst is one of the catalysts commonly used in catalytic coupling reaction, has the characteristics of high conversion rate, strong selectivity, stable performance and the like, can be used for a plurality of reactions under lower temperature and pressure conditions, and has the advantages of simple production process, no pollution, mild reaction conditions, small feeding ratio during use, recycling and the like.
The current patent (such as CN1944419A, CN110563678A, CN111620769A, CN 101607894A) related to 3,3', 4' -biphenyl tetracarboxylic acid reports mostly related to the synthesis process thereof, and relates to a small preparation method of the noble metal palladium-carbon catalyst. Of these, the patents CN1944419a and CN110563678A only mention that the catalyst used is palladium carbon-zinc, nickel palladium carbon or palladium carbon, and do not relate to a specific preparation method of the catalyst. Patent CN101607894a uses a palladium-carbon-potassium iodide binary composite catalyst in the synthesis of 3,3', 4' -biphenyltetracarboxylic acid, and the preferred preparation method of the palladium-carbon-potassium iodide binary composite catalyst is as follows: dissolving solid KI in a methanol aqueous solution with the concentration of less than or equal to 50%, adding a palladium-carbon catalyst with the concentration of 1-4% into the solution, heating to 40-70 ℃ and stirring, adding activated carbon, stirring and cooling, wherein the KI is 1-4% of the palladium-carbon catalyst, namely the activated carbon=1:2-5:2-5, filtering and drying to obtain the palladium-carbon-potassium iodide binary composite catalyst. Patent CN111620769A discloses a palladium-copper carbon supported catalyst used in the synthesis of 3,3', 4' -biphenyl tetracarboxylic acid, which is prepared by immersing 5% palladium carbon in a copper chloride aqueous solution, adjusting the pH to 11 with a sodium hydroxide aqueous solution, standing for 1-2h, stirring and heating, adding a sodium formate aqueous solution at 80-100 ℃, carrying out heat preservation reaction for 8-12 h, cooling to room temperature, filtering and washing to obtain the palladium-copper carbon supported catalyst. The preparation of the two catalysts adopts a method for carrying out post-treatment on palladium-carbon, the process is complex and time-consuming, the operation is inconvenient, and the auxiliary agent is easy to be lost when adsorbed on the surface of the palladium-carbon. Therefore, a palladium-carbon catalyst which is simple to operate and has good activity and stability is developed, and the method has very important significance for synthesizing 3,3', 4' -biphenyl tetracarboxylic acid.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the catalyst for producing 3,3',4,4' -biphenyl tetracarboxylic acid and the preparation method thereof, wherein the organic nitrogen-containing compound is added as a structure directing agent and ammonia water is used for regulating and controlling pH to prepare the composite carrier MgO-CaO/C, so that the acting force between noble metal palladium and the carrier is improved, the high dispersion of metal components is ensured, the metal is not easy to run off in the use process, and the reaction activity of the catalyst is high.
The catalyst for producing 3,3',4,4' -biphenyl tetracarboxylic acid comprises a carrier and active component palladium loaded on the carrier, wherein the content of the palladium in the catalyst is 3-5% by weight percent, and the rest is the carrier;
the carrier is an MgO-CaO/C composite carrier composed of MgO, caO and active carbon, wherein the content of MgO in the carrier is 2-5wt%, the content of CaO is 1-5wt% and the balance is active carbon according to the weight ratio of 100%.
Preferably, the activated carbon is wood powder activated carbon with specific surface area of 800-1600 m 2 And/g, the granularity is 200-400 meshes.
The preparation method of the catalyst comprises the following steps:
(1) Preparing a carrier: dissolving magnesium salt and calcium salt in pure water, adding active carbon, adding an organic nitrogen-containing compound solution to form mixed slurry, regulating the pH of the mixed slurry to 9-12 by ammonia water, stirring at room temperature for reaction for 8-12 h, filtering the obtained product, drying and calcining to obtain the MgO-CaO/C composite carrier;
(2) Preparing an active component precursor solution: dissolving sodium chloropalladate in deionized water, and regulating the pH to 3-6 by using alkali solution to obtain an active component precursor solution;
(3) Preparing palladium-containing slurry: adding the MgO-CaO/C composite carrier obtained in the step (1) into the active component precursor solution, and stirring at a constant temperature of 40-80 ℃ for 2-6 hours to obtain palladium-containing slurry;
(4) Preparing a catalyst: and adding a reducing agent into the palladium-containing slurry for reduction, filtering, and washing with deionized water until no chloride ions exist, thereby obtaining the catalyst.
Preferably, the magnesium salt is magnesium chloride and the calcium salt is calcium chloride.
Preferably, the organic nitrogen-containing compound is hexamethylenetetramine, N-dimethylformamide, ethylenediamine.
Preferably, the dosage of the organic nitrogen-containing compound accounts for 2-10% of the mass of the MgO-CaO/C composite carrier.
Preferably, the alkali solution is sodium hydroxide solution, sodium carbonate solution or sodium bicarbonate solution; the concentration of the alkali solution is 5-20wt%.
Preferably, the reducing agent is hydroxylamine hydrochloride solution or hydroxylamine sulfate solution.
Preferably, the concentration of the hydroxylamine hydrochloride solution or the hydroxylamine sulfate solution is 5-15wt%; the molar quantity of hydroxylamine hydrochloride or hydroxylamine sulfate is 1-3 times of the molar quantity of palladium.
Preferably, the calcining temperature is 500-700 ℃; the calcination time is 2-4 hours.
The invention has the advantages that:
(1) According to the invention, through preparing the MgO-CaO/C composite carrier, the unique structural characteristics of the active carbon, the magnesium oxide and the calcium oxide are effectively utilized, the adsorption of active components is facilitated, the active components of the catalyst are distributed in a larger range, and the active components of the catalyst play an important role in the dispersion and stability of the catalyst;
(2) According to the invention, by adding organic nitrogen-containing compounds such as hexamethylenetetramine, N-dimethylformamide and ethylenediamine as structure guiding agents, on one hand, the morphology distribution of MgO-CaO on activated carbon is controlled, and on the other hand, the surface groups of an activated carbon carrier are simultaneously modified, and after the carrier and an active metal salt solution are mixed, the surface of the composite carrier can provide chelating sites with metal palladium ions, so that the uniform distribution of the metal palladium ions is facilitated, and the activity of a catalyst is improved;
(3) According to the invention, the preparation of the MgO-CaO/C composite carrier overcomes the defects that the traditional activated carbon carrier is pretreated and then loaded with metal ions, and in the process of preparing the MgO-CaO/C composite carrier, the organic nitrogen-containing compound and ammonia water are used, so that the carrier generates special structure and surface property, the deposition and precipitation of metal palladium ions on the surface of the carrier are facilitated, and no alkaline solution is needed to be additionally added for precipitation, thereby simplifying the process;
(4) The prepared MgO-CaO/C composite carrier is directly added into a palladium precursor solution, hydroxylamine hydrochloride or hydroxylamine sulfate is used for reduction, the use amount of a reducing agent is controlled, the reduction degree of an active metal component on the surface of the carrier is controlled, and the activity of a catalyst can be effectively improved in the reaction;
(5) According to the invention, the MgO-CaO/C composite carrier is prepared, the precursor solution of palladium is prepared, hydroxylamine hydrochloride or hydroxylamine sulfate is used for controlling the reduction degree, so that the activity of the catalyst is improved, the adsorption stability of palladium ions is enhanced, and compared with a palladium-carbon catalyst modified by directly adding a metal-assisted salt solution, the metal-supported catalyst has stronger adsorption, and unstable catalyst performance caused by metal-assisted loss is avoided.
Detailed Description
Example 1
1. The catalyst for producing 3,3',4,4' -biphenyl tetracarboxylic acid comprises a carrier and an active component palladium supported on the carrier, wherein the content of the palladium in the catalyst is 5 percent and the content of the carrier is 95 percent according to the weight ratio of 100 percent;
wherein the carrier is an MgO-CaO/C composite carrier composed of MgO, caO and active carbon, and the weight ratio of the MgO to the CaO is 100%, wherein the content of MgO in the carrier is 2wt%, the content of CaO is 1%, and the content of active carbon is 97%;
the activated carbon is wood powder activated carbon with specific surface area of 800m 2 And/g, the granularity is 200-400 meshes.
2. The preparation method of the catalyst comprises the following steps:
(1) Preparing a carrier: 2.02g of MgCl 2 ·6H 2 O and 0.40g CaCl 2 Dissolving in pure water, adding 19.4g of active carbon, adding an aqueous solution containing 0.4g of hexamethylenetetramine to form mixed slurry, regulating the pH of the mixed slurry to 9 by ammonia water, stirring at room temperature for reaction for 8 hours, filtering the obtained product, drying, and calcining at 500 ℃ for 4 hours to obtain 20g of MgO-CaO/C composite carrier;
(2) Preparing an active component precursor solution: dissolving 0.5g (4.70 mmol, atomic mass of palladium is calculated according to 106.42) of sodium chloropalladate in deionized water, stirring until solid substances are completely dissolved, and regulating the pH to 3.0 by using 5wt% sodium hydroxide aqueous solution to obtain an active component precursor solution;
(3) Preparing palladium-containing slurry: adding 9.5g of the MgO-CaO/C composite carrier obtained in the step (1) into the active component precursor solution, and stirring at a constant temperature of 40 ℃ for 2 hours to obtain palladium-containing slurry;
(4) Preparing a catalyst: taking 0.327g (4.70 mmol) of hydroxylamine hydrochloride to prepare 5wt% aqueous solution, adding the aqueous solution into the palladium-containing slurry in the step (3), reducing, filtering, washing with deionized water until no chloride ions exist, and obtaining the catalyst which is 5% Pd/MgO-CaO/C catalyst.
Example 2
1. The catalyst for producing 3,3',4,4' -biphenyl tetracarboxylic acid comprises a carrier and an active component palladium supported on the carrier, wherein the content of the palladium in the catalyst is 4 percent and the content of the carrier is 96 percent according to the weight ratio of 100 percent;
wherein the carrier is an MgO-CaO/C composite carrier composed of MgO, caO and active carbon, and the weight ratio of the MgO to the CaO is 100%, wherein the content of MgO in the carrier is 3wt%, the content of CaO is 3%, and the content of active carbon is 94%;
the activated carbon is wood powder activated carbon with specific surface area of 1000m 2 And/g, the granularity is 200-400 meshes.
2. The preparation method of the catalyst comprises the following steps:
(1) Preparing a carrier: 3.03g of MgCl 2 ·6H 2 O and 1.19g CaCl 2 Dissolving in pure water, adding 18.8g of active carbon, adding an aqueous solution containing 1.2g of N, N-dimethylformamide to form mixed slurry, regulating the pH of the mixed slurry to 10 by ammonia water, stirring at room temperature for reaction for 10 hours, filtering the obtained product, drying, and calcining at 600 ℃ for 3 hours to obtain MgO-CaO/C composite carrier 20g;
(2) Preparing an active component precursor solution: after 0.4g (3.76 mmol) of sodium chloropalladate containing palladium is dissolved in deionized water and stirred until all solid substances are dissolved, the pH is adjusted to 4.5 by 15wt% of sodium bicarbonate aqueous solution to obtain an active component precursor solution;
(3) Preparing palladium-containing slurry: adding 9.6g of the MgO-CaO/C composite carrier obtained in the step (1) into the active component precursor solution, and stirring at a constant temperature of 60 ℃ for 4 hours to obtain palladium-containing slurry;
(4) Preparing a catalyst: 1.234g (7.52 mmol) of hydroxylamine sulfate is prepared into 10wt% aqueous solution, and is added into the palladium-containing slurry in the step (3), and the aqueous solution is reduced, filtered, washed with deionized water until no chloride ions exist, so as to obtain the catalyst, namely a 4% Pd/MgO-CaO/C catalyst.
Example 3
1. The catalyst for producing 3,3',4,4' -biphenyl tetracarboxylic acid comprises a carrier and an active component palladium supported on the carrier, wherein the content of the palladium in the catalyst is 3 percent and the content of the carrier is 97 percent according to the weight ratio of 100 percent;
wherein the carrier is an MgO-CaO/C composite carrier composed of MgO, caO and active carbon, and the weight ratio of the MgO to the CaO is 100%, wherein the content of MgO in the carrier is 5wt%, the content of CaO is 5%, and the content of active carbon is 90%;
the activated carbon is wood powder activated carbon with a specific surface area of 1600m 2 And/g, the granularity is 200-400 meshes.
2. The preparation method of the catalyst comprises the following steps:
(1) Preparing a carrier: 5.04g of MgCl 2 ·6H 2 O and 1.98g CaCl 2 Dissolving in pure water, adding 18.0g of active carbon, adding an aqueous solution containing 2.0g of ethylenediamine to form a mixed slurry, regulating the pH of the mixed slurry to 12 by ammonia water, stirring at room temperature for reaction for 12 hours, filtering the obtained product, drying, and calcining at 700 ℃ for 2 hours to obtain the MgO-CaO/C composite carrier 20g;
(2) Preparing an active component precursor solution: after 0.3g (2.82 mmol) of sodium chloropalladate containing palladium is dissolved in deionized water and stirred until all solid matters are dissolved, 10wt% of sodium carbonate aqueous solution is used for regulating the pH value to 6.0, and an active component precursor solution is obtained;
(3) Preparing palladium-containing slurry: adding 9.7g of the MgO-CaO/C composite carrier obtained in the step (1) into the active component precursor solution, and stirring at a constant temperature of 80 ℃ for 6 hours to obtain palladium-containing slurry;
(4) Preparing a catalyst: 1.389g (8.46 mmol) of hydroxylamine sulfate is prepared into 15wt% aqueous solution, and is added into the palladium-containing slurry in the step (3), and the aqueous solution is reduced, filtered, washed with deionized water until no chloride ions exist, so as to obtain the catalyst which is 3% Pd/MgO-CaO/C catalyst.
Example 4
1. The catalyst for producing 3,3',4,4' -biphenyl tetracarboxylic acid comprises a carrier and an active component palladium supported on the carrier, wherein the content of the palladium in the catalyst is 4.5 percent and the content of the carrier is 95.5 percent according to the weight ratio of 100 percent;
wherein the carrier is an MgO-CaO/C composite carrier composed of MgO, caO and active carbon, and the weight ratio of the MgO to the CaO is 100%, wherein the content of MgO in the carrier is 5wt%, the content of CaO is 3%, and the content of active carbon is 92%;
the activated carbon is wood powder activated carbon with a specific surface area of 1300m 2 And/g, the granularity is 200-400 meshes.
2. The preparation method of the catalyst comprises the following steps:
(1) Preparing a carrier: 5.04g of MgCl 2 ·6H 2 O and 1.19g CaCl 2 Dissolving in pure water, adding 18.4g of active carbon, adding an aqueous solution containing 1.0g of hexamethylenetetramine to form a mixed slurry, regulating the pH of the mixed slurry to 10.5 by ammonia water, stirring at room temperature for reaction for 8 hours, filtering the obtained product, drying, and calcining at 650 ℃ for 3 hours to obtain the MgO-CaO/C composite carrier 20g;
(2) Preparing an active component precursor solution: after 0.45g (4.23 mmol) of sodium chloropalladate containing palladium is dissolved in deionized water and stirred until all solid substances are dissolved, the pH is adjusted to 3.5 by 5wt% of sodium bicarbonate aqueous solution to obtain an active component precursor solution;
(3) Preparing palladium-containing slurry: adding 9.65g of the MgO-CaO/C composite carrier obtained in the step (1) into the active component precursor solution, and stirring at a constant temperature of 70 ℃ for 3 hours to obtain palladium-containing slurry;
(4) Preparing a catalyst: and (3) preparing 0.882g (12.69 mmol) of hydroxylamine hydrochloride into a 10wt% aqueous solution, adding the aqueous solution into the palladium-containing slurry obtained in the step (3), reducing, filtering, washing with deionized water until no chloride ions exist, and obtaining the catalyst which is 4.5% Pd/MgO-CaO/C catalyst.
Example 5
1. The catalyst for producing 3,3',4,4' -biphenyl tetracarboxylic acid comprises a carrier and an active component palladium supported on the carrier, wherein the content of the palladium in the catalyst is 3.5 percent and the content of the carrier is 96.5 percent according to the weight ratio of 100 percent;
wherein the carrier is an MgO-CaO/C composite carrier composed of MgO, caO and active carbon, and the weight ratio of the MgO to the CaO is 100%, wherein the content of MgO in the carrier is 3wt%, the content of CaO is 4%, and the content of active carbon is 93%;
the activated carbon is wood powder activated carbon with specific surface area of 1000m 2 And/g, the granularity is 200-400 meshes.
2. The preparation method of the catalyst comprises the following steps:
(1) Manufacturing processPreparing a carrier: 3.03g of MgCl 2 ·6H 2 O and 1.58g CaCl 2 Dissolving in pure water, adding 18.6g of active carbon, adding an aqueous solution containing 0.8g of ethylenediamine to form a mixed slurry, regulating the pH of the mixed slurry to 10 by using ammonia water, stirring at room temperature for reaction for 8 hours, filtering the obtained product, drying, and calcining at 550 ℃ for 2 hours to obtain the MgO-CaO/C composite carrier 20g;
(2) Preparing an active component precursor solution: after 0.35g (3.29 mmol) of sodium chloropalladate containing palladium is dissolved in deionized water and stirred until all solid substances are dissolved, the pH is adjusted to 4.5 by using 20wt% of sodium bicarbonate aqueous solution, and an active component precursor solution is obtained;
(3) Preparing palladium-containing slurry: adding 9.65g of the MgO-CaO/C composite carrier obtained in the step (1) into the active component precursor solution, and stirring at a constant temperature of 50 ℃ for 6 hours to obtain palladium-containing slurry;
(4) Preparing a catalyst: 1.08g (6.58 mmol) of hydroxylamine sulfate is prepared into 5wt% aqueous solution, and is added into the palladium-containing slurry in the step (3), and the aqueous solution is reduced, filtered, washed with deionized water until no chloride ions exist, so as to obtain the catalyst, namely the 3.5% Pd/MgO-CaO/C catalyst.
Comparative example 1
The carrier adopts active carbon to directly replace MgO-CaO/C composite carrier, and other preparation methods are the same as in example 2, so as to obtain the 4% Pd/C catalyst.
Comparative example 2
Step (1) was carried out in the same manner as in example 2 except that N, N-dimethylformamide as a nitrogen-containing organic compound was not added, thereby obtaining a 4% Pd/MgO-CaO/C catalyst.
Comparative example 3
MgCl is not added in the step (1) 2 ·6H 2 O and CaCl 2 The mass of the activated carbon was 20g, and the other preparation steps were the same as in example 2, to obtain a 4% Pd/C catalyst.
Comparative example 4
In the step (1), the pH of the mixed slurry was not adjusted, and the other preparation steps were the same as in example 2 to obtain a 4% Pd/MgO-CaO/C catalyst.
Comparative example 5
In the step (4), sodium borohydride was used instead of hydroxylamine sulfate, and the other preparation steps were the same as in example 2 to obtain a 4% Pd/MgO-CaO/C catalyst.
Comparative example 6
MgCl is not added in the step (1) 2 ·6H 2 The mass of O and activated carbon was 19.6g, and the other preparation steps were the same as in example 2 to obtain a 4% Pd/CaO/C catalyst.
Comparative example 7
CaCl is not added in the step (1) 2 The mass of the activated carbon was 19.6g, and the other preparation steps were the same as in example 2, to obtain a 4% Pd/MgO/C catalyst.
Catalytic performance detection
The catalysts provided in examples and comparative examples were used to synthesize 3,3',4,4' -biphenyltetracarboxylic acid as follows: adding 60g of water and 12g of NaOH into a four-neck flask with a thermometer, a stirrer, a dripping peristaltic pump and a reflux device, adding 15g of 4-chlorophthalic acid and 0.1g of catalyst (dry basis) under stirring, heating to 100 ℃ for reflux, dripping a mixed solution of 5.2g of hydrazine sulfate and 20g of water, controlling the dripping speed, keeping a reflux state, and dripping for 2 hours; after the completion of the dropwise addition, the reaction was stopped after 5 hours of incubation, the reaction mixture was taken out, the catalyst was removed by filtration, and the filtrate was analyzed by liquid chromatography, and the results are shown in Table 1.
TABLE 1 chromatographic analysis of the 3,3',4,4' -biphenyltetracarboxylic acid reaction product
As can be seen from Table 1, the catalyst of the present invention has higher activity, and compared with example 2, the catalyst of comparative example 1 directly using activated carbon as a carrier, i.e., without using MgO-CaO/C composite carrier, has very low raw material conversion rate and product yield; while comparative example 2 in which no organic nitrogen-containing compound was added in step (1), comparative examples 3, 6, and 7 in which no magnesium and/or calcium salt was added in step (1), and comparative example 5 in which sodium borohydride was used as the reducing agent instead of hydroxylamine hydrochloride or hydroxylamine sulfate, both the raw material conversion rate and the product yield were low; in comparative example 4 in which the precursor solution was not adjusted in pH, the conversion of raw materials and the yield of products were lowered, and in comparative example 4, the performance of the catalyst was improved considerably as compared with comparative example 1. Therefore, the MgO-CaO/C composite carrier prepared by adopting the organic nitrogen-containing compound as the auxiliary agent can improve the activity of the palladium catalyst; the active component solution is regulated to a certain pH value, and the performance of the catalyst is also influenced to a certain extent; the reducing agent also has a great influence on the performance of the catalyst. When the catalyst is provided with the catalyst, the activity of the catalyst is obviously improved, and the performance of the catalyst is optimal.
Claims (7)
1. A method for preparing a catalyst for producing 3,3',4,4' -biphenyl tetracarboxylic acid, which is characterized by comprising the following steps: the catalyst comprises a carrier and active component palladium loaded on the carrier, wherein the content of the palladium in the catalyst is 3-5% by weight of the catalyst, and the balance is the carrier;
wherein the carrier is an MgO-CaO/C composite carrier composed of MgO, caO and active carbon, and the weight ratio of the MgO to the CaO is 100 percent, the content of MgO in the carrier is 2 to 5 percent by weight, the content of CaO is 1 to 5 percent by weight, and the balance is active carbon;
the preparation method comprises the following steps:
(1) Preparing a carrier: dissolving magnesium salt and calcium salt in pure water, adding active carbon, adding an organic nitrogen-containing compound solution to form mixed slurry, regulating the pH of the mixed slurry to 9-12 by ammonia water, stirring at room temperature for reaction for 8-12 h, filtering the obtained product, drying and calcining to obtain the MgO-CaO/C composite carrier;
(2) Preparing an active component precursor solution: dissolving sodium chloropalladate in deionized water, and regulating the pH to 3-6 by using alkali solution to obtain an active component precursor solution;
(3) Preparing palladium-containing slurry: adding the MgO-CaO/C composite carrier obtained in the step (1) into the active component precursor solution, and stirring at a constant temperature of 40-80 ℃ for 2-6 hours to obtain palladium-containing slurry;
(4) Preparing a catalyst: adding a reducing agent into the palladium-containing slurry for reduction, filtering, and washing with deionized water until no chloride ions exist, so as to obtain the catalyst;
the organic nitrogen-containing compound is hexamethylenetetramine, N-dimethylformamide or ethylenediamine;
the reducing agent is hydroxylamine hydrochloride solution or hydroxylamine sulfate solution.
2. The method for producing a catalyst for 3,3',4,4' -biphenyltetracarboxylic acid as defined in claim 1, wherein: the activated carbon is wood powder activated carbon, and the specific surface area is 800-1600 m 2 And/g, the granularity is 200-400 meshes.
3. The method for producing a catalyst for 3,3',4,4' -biphenyltetracarboxylic acid as claimed in claim 2, wherein: the magnesium salt is magnesium chloride, and the calcium salt is calcium chloride.
4. The method for producing a catalyst for 3,3',4,4' -biphenyltetracarboxylic acid as recited in claim 3, wherein: the dosage of the organic nitrogen-containing compound accounts for 2-10% of the mass of the MgO-CaO/C composite carrier.
5. The method for producing a catalyst for 3,3',4,4' -biphenyltetracarboxylic acid as recited in claim 3, wherein: the alkali solution is sodium hydroxide solution, sodium carbonate solution or sodium bicarbonate solution; the concentration of the alkali solution is 5-20wt%.
6. The method for producing a catalyst for 3,3',4,4' -biphenyltetracarboxylic acid as recited in claim 5, wherein: the concentration of the hydroxylamine hydrochloride solution or the hydroxylamine sulfate solution is 5-15wt%; the molar quantity of hydroxylamine hydrochloride or hydroxylamine sulfate is 1-3 times of the molar quantity of palladium.
7. The method for producing a catalyst for 3,3',4,4' -biphenyltetracarboxylic acid as recited in claim 5, wherein: the calcination temperature is 500-700 ℃, and the calcination time is 2-4 hours.
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