CN115433104A - Preparation method of decanedinitrile - Google Patents
Preparation method of decanedinitrile Download PDFInfo
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- CN115433104A CN115433104A CN202211008198.9A CN202211008198A CN115433104A CN 115433104 A CN115433104 A CN 115433104A CN 202211008198 A CN202211008198 A CN 202211008198A CN 115433104 A CN115433104 A CN 115433104A
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- sebacic acid
- phosphorus pentoxide
- catalyst
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- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- DFJYZCUIKPGCSG-UHFFFAOYSA-N decanedinitrile Chemical compound N#CCCCCCCCCC#N DFJYZCUIKPGCSG-UHFFFAOYSA-N 0.000 title claims abstract description 30
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims abstract description 106
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims abstract description 96
- 239000003054 catalyst Substances 0.000 claims abstract description 78
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 44
- 239000000047 product Substances 0.000 claims abstract description 33
- 239000000203 mixture Substances 0.000 claims abstract description 26
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000012043 crude product Substances 0.000 claims abstract description 13
- 238000011049 filling Methods 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims description 34
- 238000002156 mixing Methods 0.000 claims description 19
- 239000011259 mixed solution Substances 0.000 claims description 17
- 239000002243 precursor Substances 0.000 claims description 17
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 14
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 230000032683 aging Effects 0.000 claims description 11
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 11
- 238000001694 spray drying Methods 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 238000004537 pulping Methods 0.000 claims description 10
- 239000002002 slurry Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000001556 precipitation Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 150000001879 copper Chemical class 0.000 claims description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 6
- 159000000003 magnesium salts Chemical class 0.000 claims description 6
- 150000003751 zinc Chemical class 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 3
- 239000011654 magnesium acetate Substances 0.000 claims description 3
- 235000011285 magnesium acetate Nutrition 0.000 claims description 3
- 229940069446 magnesium acetate Drugs 0.000 claims description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 3
- 239000012716 precipitator Substances 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 230000000052 comparative effect Effects 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 5
- 238000009776 industrial production Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000012024 dehydrating agents Substances 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- SGRHVVLXEBNBDV-UHFFFAOYSA-N 1,6-dibromohexane Chemical compound BrCCCCCCBr SGRHVVLXEBNBDV-UHFFFAOYSA-N 0.000 description 2
- LOVRXPMGNOQIEC-UHFFFAOYSA-N P(=O)(O)(O)O.C(C)C=1N=C(NC1)C Chemical compound P(=O)(O)(O)O.C(C)C=1N=C(NC1)C LOVRXPMGNOQIEC-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- QAEDZJGFFMLHHQ-UHFFFAOYSA-N trifluoroacetic anhydride Chemical compound FC(F)(F)C(=O)OC(=O)C(F)(F)F QAEDZJGFFMLHHQ-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000005915 ammonolysis reaction Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 238000007333 cyanation reaction Methods 0.000 description 1
- VDBXLXRWMYNMHL-UHFFFAOYSA-N decanediamide Chemical compound NC(=O)CCCCCCCCC(N)=O VDBXLXRWMYNMHL-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000002085 irritant Substances 0.000 description 1
- 231100000021 irritant Toxicity 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/22—Preparation of carboxylic acid nitriles by reaction of ammonia with carboxylic acids with replacement of carboxyl groups by cyano groups
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/32—Separation; Purification; Stabilisation; Use of additives
- C07C253/34—Separation; Purification
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of preparation of decanedinitrile, and particularly relates to a preparation method of decanedinitrile. The preparation method comprises the following steps: s1, selecting ZnCuMg/Al 2 O 3 The mixture of the catalyst and phosphorus pentoxide is used as a catalyst bed layer; s2, filling the catalyst bed layer prepared in the step S1 into a fixed bed reactor; s3, metering by a sebacic acid feeder, feeding the sebacic acid feeder into a preheating section, preheating, and feeding the preheated sebacic acid feeder and ammonia gas into a catalyst bed layer for reaction; and S4, rectifying and purifying the crude product to obtain the product of the decanedionitrile. The preparation method of the decanedionitrile has higher yield.
Description
Technical Field
The invention belongs to the technical field of preparation of decanedionitrile. More particularly, it relates to a process for the preparation of decanedinitrile.
Background
The decanedionitrile is an intermediate for organic synthesis of medicines, dyes and the like, is a chemical intermediate for synthesizing decanediamine, is an important intermediate product for producing novel fibers, films and plastic monomers, and can be used as a solvent and a plasticizer.
The existing methods for synthesizing the decanedinitrile have few reports, and mainly comprise (1) the method for preparing the decanedinitrile by using the condensation reaction of acetonitrile and 1, 6-dibromohexane, but the yield is low (50-70 percent), and the 1, 6-dibromohexane is expensive and is not beneficial to industrial production; (2) The preparation method is characterized in that sebacamide is added with trifluoroacetic anhydride dehydrating agent, but the dehydrating agent is volatile, easy to hydrolyze, irritant, and harsh in application conditions, is only suitable for preparing sebaconitrile in a laboratory, and is not beneficial to industrial production; (3) The sebacic acid is subjected to ammonolysis dehydration to prepare the sebacic dinitrile by using an intensified temperature method, wherein the intensified temperature generally exceeds more than 300 ℃, and the time is long. However, in the intensified temperature method, the organic matter is easily carbonized due to the high reaction temperature, and the number of by-products is increased.
Panyu and the like are improved relatively, sebacic acid and ammonia gas are taken as raw materials, and a composite catalyst ZnO/Al is adopted 2 O 3 The yield of the catalytic synthesis of the decanedinitrile is 83 percent and the purity is 92 percent at the temperature of 210-265 ℃ under the catalysis.
CN109206341A discloses a preparation method of decanedionitrile, which belongs to the field of organic synthesis and comprises the following steps: (1) Preparing ethyl methyl imidazole dihydrogen phosphate ionic liquid; (2) The ethyl methyl imidazole dihydrogen phosphate ionic liquid is used as a solvent and a catalyst, and is used for reducing the reaction time and temperature to a certain extent in the process of preparing sebacic dinitrile by sebacic acid cyanation, so that the side reaction of the reaction is reduced, and the yield is improved.
CN107266335A discloses a method for synthesizing decanedinitrile by a one-pot method, belonging to the field of chemical synthesis. Heating and melting sebacic acid, then adding urea in batches for condensation reaction, and after the reaction is finished, adding a high-boiling-point solvent to disperse a substrate; uniformly dispersing a substrate, and then adding a dehydrating agent at a reaction temperature to carry out dehydration reaction; after the dehydration reaction is finished, adding water to quench and stop the reaction, and then extracting and separating liquid to obtain an oil phase I; adding the oil phase I into a saturated sodium bicarbonate solution, stirring for reaction, extracting, separating to obtain an oil phase II, removing the solvent under normal pressure, and rectifying under reduced pressure to obtain a high-purity product. The method has the characteristics of mild reaction conditions, simple process flow, convenient post-treatment, high product purity, simple equipment requirement, safe operation, low cost and the like, and is an effective method easy for industrial production.
As described above, although the production of sebacic acid dinitrile is possible in the prior art, there are problems that the yield is low, the reaction needs to be carried out in a closed vessel, and the industrial production is not facilitated.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects and shortcomings in the prior art and provide aA method for preparing decanedinitrile. The preparation method comprises the following steps: s1, selecting ZnCuMg/Al 2 O 3 The mixture of the catalyst and phosphorus pentoxide is used as a catalyst bed layer; s2, filling the catalyst bed layer prepared in the step S1 into a fixed bed reactor; s3, metering by a sebacic acid feeder, entering a preheating section, preheating, and entering a catalyst bed layer together with ammonia gas for reaction; and S4, rectifying and purifying the crude product to obtain the product of the sebacic acid dinitrile. The preparation method of the decanedionitrile has higher yield.
The invention aims to provide a preparation method of decanedionitrile.
The above purpose of the invention is realized by the following technical scheme:
a process for the preparation of decanedinitrile, which comprises the steps of:
s1, selecting ZnCuMg/Al 2 O 3 The mixture of the catalyst and phosphorus pentoxide is used as a catalyst bed layer;
s2, filling the catalyst bed layer prepared in the step S1 into a fixed bed reactor;
s3, metering by a sebacic acid feeder, feeding the sebacic acid feeder into a preheating section, preheating, and feeding the preheated sebacic acid feeder and ammonia gas into a catalyst bed layer for reaction;
and S4, rectifying and purifying the crude product to obtain the product of the decanedionitrile.
Preferably, in the S1 step, znCuMg/Al 2 O 3 The mass ratio of the phosphorus pentoxide to the phosphorus pentoxide is 1.2-0.4; the molar ratio of zinc, copper, magnesium and aluminum is 1: 0.02-0.06.
Preferably, in the step S3, the preheating temperature is 120 to 240 ℃, and the reaction conditions are as follows: the molar ratio of sebacic acid to ammonia gas is: 1:2 to 7; the reaction pressure is 0.1-1 Mpa, the space velocity of the sebacic acid is 0.4-1.2 h -1 。
Preferably, the ZnCuMg/Al 2 O 3 The preparation method comprises the following steps:
dissolving zinc salt, copper salt and magnesium salt in deionized water to prepare a mixed solution, then slowly dropwise adding a precipitator into the mixed solution under the stirring condition, and controlling the pH value to be 9-10; aging, washing to obtain precursor, and mixingMixing the driver and aluminum hydroxide for pulping to obtain catalyst slurry; spray drying and calcining to obtain the product ZnCuMg/Al 2 O 3 。
Preferably, the molar ratio of the zinc salt, the copper salt, the magnesium salt and the aluminum hydroxide is 1: 0.02-0.06.
Preferably, the zinc salt is at least one of zinc nitrate, zinc acetate and zinc chloride; the copper salt is at least one of copper nitrate, copper acetate and copper chloride; the magnesium salt is at least one of magnesium nitrate, magnesium acetate and magnesium chloride.
Preferably, the precipitant is at least one of sodium hydroxide solution, potassium hydroxide solution and sodium carbonate solution; the concentration of the precipitant is 2-4 mol/L.
Preferably, the temperature of the precipitation process is 50-70 ℃; the aging time is 30-60 min.
Preferably, the roasting conditions are as follows: roasting at 500-600 deg.c for 0.5-1.5 hr.
Preferably, the ZnCuMg/Al 2 O 3 The mixture with phosphorus pentoxide is prepared by mixing ZnCuMg/Al 2 O 3 And stirring and mixing the mixture and phosphorus pentoxide at the mass ratio of 1.2-0.4 to obtain a mixture.
The invention has the following beneficial effects:
(1) Preparation of ZnCuMg/Al by coprecipitation method in combination with spray drying 2 O 3 The catalyst, through modification of copper and magnesium, improves the conversion rate of raw materials and the selectivity of products, and further influences the yield;
(2) By ZnCuMg/Al 2 O 3 The catalyst is compounded with phosphorus pentoxide, so that the yield of the product is further improved;
(3) The catalyst of the invention is simple to prepare, cheap and easy to obtain; the reaction raw materials are cheap and pollution-free.
Detailed Description
The present invention will be further described with reference to the following specific examples, which are not intended to limit the invention in any manner. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Unless otherwise indicated, reagents and materials used in the following examples are commercially available.
Example 1
A method for preparing decanedinitrile, which is characterized by comprising the following steps: the preparation method comprises the following steps:
s1, selecting 1kg of ZnCuMg/Al 2 O 3 The mixture of the catalyst and phosphorus pentoxide is used as a catalyst bed layer;
s2, filling the catalyst bed layer prepared in the step S1 into a fixed bed reactor;
s3, metering by a sebacic acid feeder, feeding the mixture into a preheating section, preheating at 220 ℃, and feeding the preheated mixture and ammonia gas into a catalyst bed layer for reaction; the reaction conditions are as follows: the molar ratio of sebacic acid to ammonia gas is: 1:4; the reaction pressure is 0.6Mpa, and the space velocity of the sebacic acid is 1h -1 ；
And S4, rectifying and purifying the crude product to obtain the product of the sebacic acid dinitrile. ZnCuMg/Al 2 O 3 The mass ratio of the phosphorus pentoxide to the phosphorus pentoxide is 1.
Wherein, the ZnCuMg/Al 2 O 3 The preparation method comprises the following steps:
dissolving 0.1mol of zinc nitrate, 0.004mol of copper nitrate and 0.009mol of magnesium nitrate in 100mL of deionized water to prepare a mixed solution, then slowly dropwise adding 3mol/L of a hydroxide solution into the mixed solution under the stirring condition, controlling the temperature in the precipitation process to be 60 ℃ and controlling the pH value to be 10; aging for 50min, washing to obtain a precursor, and then mixing and pulping the precursor and 0.3mol of aluminum hydroxide to obtain catalyst slurry; spray drying, calcining at 550 ℃ for 1h to obtain the product ZnCuMg/Al 2 O 3 ；
The obtained ZnCuMg/Al 2 O 3 And mixing the catalyst and phosphorus pentoxide uniformly to obtain the catalyst. The mass ratio of the product A to the phosphorus pentoxide is 1.
Example 2
A method for preparing decanedinitrile, which is characterized in that: the preparation method comprises the following steps:
s1, selecting 1kg of ZnCuMg/Al 2 O 3 The mixture of the catalyst and phosphorus pentoxide is used as a catalyst bed layer;
s2, filling the catalyst bed layer prepared in the step S1 into a fixed bed reactor;
s3, metering by a sebacic acid feeder, feeding the sebacic acid feeder into a preheating section, preheating at 240 ℃, and feeding the preheated sebacic acid feeder and ammonia gas into a catalyst bed layer for reaction; the reaction conditions are as follows: the molar ratio of sebacic acid to ammonia gas is: 1:7; the reaction pressure is 1Mpa, and the space velocity of the sebacic acid is 1.2h -1 ；
And S4, rectifying and purifying the crude product to obtain the product of the decanedionitrile. ZnCuMg/Al 2 O 3 The mass ratio of the phosphorus pentoxide to the phosphorus pentoxide is 1.
Wherein, the ZnCuMg/Al 2 O 3 The preparation method comprises the following steps:
dissolving 0.1mol of zinc chloride, 0.006mol of copper acetate and 0.006mol of magnesium nitrate in 100mL of deionized water to prepare a mixed solution, then slowly dropwise adding 4mol/L of potassium hydroxide solution into the mixed solution under the stirring condition, wherein the temperature in the precipitation process is 70 ℃, and the pH value is controlled to be 9; aging for 60min, washing to obtain a precursor, and then mixing and pulping the precursor and 0.4mol of aluminum hydroxide to obtain catalyst slurry; through spray drying and calcining at 600 ℃ for 0.5h, the product ZnCuMg/Al is obtained 2 O 3 ；
The obtained ZnCuMg/Al 2 O 3 And mixing the catalyst with phosphorus pentoxide uniformly to obtain the catalyst. The mass ratio of the product A to the phosphorus pentoxide is 1.
Example 3
A method for preparing decanedinitrile, which is characterized in that: the preparation method comprises the following steps:
s1, selecting 1kg of ZnCuMg/Al 2 O 3 The mixture of the catalyst and phosphorus pentoxide is used as a catalyst bed layer;
s2, filling the catalyst bed layer prepared in the step S1 into a fixed bed reactor;
s3, metering by a sebacic acid feeder, feeding the sebacic acid feeder into a preheating section, preheating at 200 ℃, and feeding the preheated sebacic acid feeder and ammonia gas into a catalyst bed layer for reaction; the reaction conditions are as follows: sebacic acid and ammoniaThe molar ratio of (A) to (B): 1:2.5; the reaction pressure is 0.2Mpa, and the space velocity of the sebacic acid is 0.4h -1
And S4, rectifying and purifying the crude product to obtain the product of the sebacic acid dinitrile. ZnCuMg/Al 2 O 3 The mass ratio of the phosphorus pentoxide to the phosphorus pentoxide is 1;
wherein, the ZnCuMg/Al 2 O 3 The preparation method comprises the following steps:
dissolving 0.1mol of zinc acetate, 0.002mol of magnesium acetate and 0.012mol of magnesium chloride in 100mL of deionized water to prepare a mixed solution, then slowly dropwise adding 2mol/L of sodium carbonate solution into the mixed solution under the stirring condition, wherein the temperature in the precipitation process is 50 ℃, and the pH value is controlled to be 10; aging for 30min, washing to obtain a precursor, and then mixing and pulping the precursor and 0.2mol of aluminum hydroxide to obtain catalyst slurry; spray drying, calcining at 500 ℃ for 1.5h to obtain the product ZnCuMg/Al 2 O 3 ；
The obtained ZnCuMg/Al 2 O 3 And mixing the catalyst with phosphorus pentoxide uniformly to obtain the catalyst. The mass ratio of the product A to the phosphorus pentoxide is 1.
Comparative example 1
A method for preparing decanedinitrile, which is characterized by comprising the following steps: the preparation method comprises the following steps:
s1, selecting 1kg ZnCu/Al 2 O 3 The mixture of the catalyst and phosphorus pentoxide is used as a catalyst bed layer;
s2, filling the catalyst bed layer prepared in the step S1 into a fixed bed reactor;
s3, metering by a sebacic acid feeder, feeding the sebacic acid feeder into a preheating section, preheating at 220 ℃, and feeding the preheated sebacic acid feeder and ammonia gas into a catalyst bed layer for reaction; the reaction conditions are as follows: the molar ratio of sebacic acid to ammonia gas is: 1:4; the reaction pressure is 0.6Mpa, and the space velocity of the sebacic acid is 1h -1 ；
And S4, rectifying and purifying the crude product to obtain the product of the decanedionitrile. ZnCu/Al 2 O 3 The mass ratio of the phosphorus pentoxide to the phosphorus pentoxide is 1.
Wherein, the ZnCu/Al 2 O 3 The preparation method comprises the following steps:
dissolving 0.1mol of zinc nitrate and 0.013mol of copper nitrate in 100mL of deionized water to prepare a mixed solution, then slowly dropwise adding 3mol/L of a hydroxide solution into the mixed solution under the stirring condition, controlling the temperature in the precipitation process to be 60 ℃ and controlling the pH value to be 10; aging for 50min, washing to obtain a precursor, and then mixing and pulping the precursor and 0.3mol of aluminum hydroxide to obtain catalyst slurry; spray drying and calcining at 550 ℃ for 1h to obtain the product ZnCu/Al 2 O 3 ；
The obtained ZnCu/Al 2 O 3 And mixing the catalyst and phosphorus pentoxide uniformly to obtain the catalyst. The mass ratio of the product A to the phosphorus pentoxide is 1.
Comparative example 2
A method for preparing decanedinitrile, which is characterized by comprising the following steps: the preparation method comprises the following steps:
s1, selecting 1kg of ZnMg/Al 2 O 3 The mixture of the catalyst and phosphorus pentoxide is used as a catalyst bed layer;
s2, filling the catalyst bed layer prepared in the step S1 into a fixed bed reactor;
s3, metering by a sebacic acid feeder, feeding the mixture into a preheating section, preheating at 220 ℃, and feeding the preheated mixture and ammonia gas into a catalyst bed layer for reaction; the reaction conditions are as follows: the molar ratio of sebacic acid to ammonia gas is: 1:4; the reaction pressure is 0.6Mpa, and the space velocity of the sebacic acid is 1h -1 ；
And S4, rectifying and purifying the crude product to obtain the product of the decanedionitrile. ZnMg/Al 2 O 3 The mass ratio of the phosphorus pentoxide to the phosphorus pentoxide is 1.
Wherein, the ZnMg/Al 2 O 3 The preparation method comprises the following steps:
dissolving 0.1mol of zinc nitrate and 0.013mol of magnesium nitrate in 100mL of deionized water to prepare a mixed solution, then slowly dropwise adding 3mol/L of a hydroxide solution into the mixed solution under the stirring condition, wherein the temperature in the precipitation process is 60 ℃, and the pH value is controlled to be 10; aging for 50min, washing to obtain a precursor, and then mixing and pulping the precursor and 0.3mol of aluminum hydroxide to obtain catalyst slurry; by spray drying and calcining at 550 ℃ for 1h to obtainProduct ZnMg/Al 2 O 3 ；
ZnMg/Al to be obtained 2 O 3 And mixing the catalyst and phosphorus pentoxide uniformly to obtain the catalyst. The mass ratio of the product A to the phosphorus pentoxide is 1.
Comparative example 3
A method for preparing decanedinitrile, which is characterized by comprising the following steps: the preparation method comprises the following steps:
s1, selecting a mixture of 1kg of ZnCuMg and phosphorus pentoxide as a catalyst bed layer;
s2, filling the catalyst bed layer prepared in the step S1 into a fixed bed reactor;
s3, metering by a sebacic acid feeder, feeding the sebacic acid feeder into a preheating section, preheating at 220 ℃, and feeding the preheated sebacic acid feeder and ammonia gas into a catalyst bed layer for reaction; the reaction conditions are as follows: the molar ratio of sebacic acid to ammonia gas is: 1:4; the reaction pressure is 0.6Mpa, and the space velocity of the sebacic acid is 1h -1 ；
And S4, rectifying and purifying the crude product to obtain the product of the sebacic acid dinitrile. The mass ratio of ZnCuMg to phosphorus pentoxide is 1.
The preparation method of ZnCuMg comprises the following steps:
dissolving 0.1mol of zinc nitrate, 0.004mol of copper nitrate and 0.009mol of magnesium nitrate in 100mL of deionized water to prepare a mixed solution, then slowly dropwise adding 3mol/L of a hydroxide solution into the mixed solution under the stirring condition, controlling the temperature in the precipitation process to be 60 ℃ and controlling the pH value to be 10; aging for 50min, washing to obtain a precursor, and pulping the precursor to obtain catalyst slurry; spray drying, calcining at 550 ℃ for 1h to obtain a product ZnCuMg;
and uniformly mixing the obtained ZnCuMg and phosphorus pentoxide to obtain the catalyst. The mass ratio of the product A to the phosphorus pentoxide is 1.
Comparative example 4
A method for preparing decanedinitrile, which is characterized in that: the preparation method comprises the following steps:
s1, selecting 1kg of Al 2 O 3 The mixture of the catalyst and phosphorus pentoxide is used as a catalyst bed layer;
s2, filling the catalyst bed layer prepared in the step S1 into a fixed bed reactor;
s3, metering by a sebacic acid feeder, feeding the mixture into a preheating section, preheating at 220 ℃, and feeding the preheated mixture and ammonia gas into a catalyst bed layer for reaction; the reaction conditions are as follows: the molar ratio of sebacic acid to ammonia gas is: 1:4; the reaction pressure is 0.6Mpa, and the space velocity of the sebacic acid is 1h -1 ；
And S4, rectifying and purifying the crude product to obtain the product of the decanedionitrile. Al (Al) 2 O 3 The mass ratio of the phosphorus pentoxide to the phosphorus pentoxide is 1.
Wherein said Al is 2 O 3 The preparation method comprises the following steps:
mixing and pulping 0.3mol of aluminum hydroxide to obtain catalyst slurry; spray drying, calcining at 550 ℃ for 1h to obtain the product Al 2 O 3 ；
The obtained Al 2 O 3 And mixing the catalyst and phosphorus pentoxide uniformly to obtain the catalyst. The mass ratio of the product A to the phosphorus pentoxide is 1.
Comparative example 5
A method for preparing decanedinitrile, which is characterized by comprising the following steps: the preparation method comprises the following steps:
s1, selecting 1kg of ZnCuMg/Al 2 O 3 Preparing a catalyst bed layer;
s2, filling the catalyst bed layer prepared in the step S1 into a fixed bed reactor;
s3, metering by a sebacic acid feeder, feeding the sebacic acid feeder into a preheating section, preheating at 220 ℃, and feeding the preheated sebacic acid feeder and ammonia gas into a catalyst bed layer for reaction; the reaction conditions are as follows: the molar ratio of sebacic acid to ammonia gas is: 1:4; the reaction pressure is 0.6Mpa, and the space velocity of the sebacic acid is 1h -1 ；
And S4, rectifying and purifying the crude product to obtain the product of the decanedionitrile.
Wherein, the ZnCuMg/Al 2 O 3 The preparation method comprises the following steps:
0.1mol of zinc nitrate, 0.004mol of copper nitrate and 0.009mol of magnesium nitrate are dissolved in 100mL of deionized water to prepare the water-soluble copper-zinc composite materialMixing the solution, then slowly dropwise adding 3mol/L of a hydroxide solution into the mixed solution under the stirring condition, wherein the temperature in the precipitation process is 60 ℃, and the pH value is controlled to be 10; aging for 50min, washing to obtain a precursor, and then mixing and pulping the precursor and 0.3mol of aluminum hydroxide to obtain catalyst slurry; spray drying, calcining at 550 ℃ for 1h to obtain the product ZnCuMg/Al 2 O 3 。
Comparative example 6
A method for preparing decanedinitrile, which is characterized by comprising the following steps: the preparation method comprises the following steps:
s1, selecting a mixture of phosphorus pentoxide as a catalyst bed layer;
s2, filling the catalyst bed layer prepared in the step S1 into a fixed bed reactor;
s3, metering by a sebacic acid feeder, feeding the mixture into a preheating section, preheating at 220 ℃, and feeding the preheated mixture and ammonia gas into a catalyst bed layer for reaction; the reaction conditions are as follows: the molar ratio of sebacic acid to ammonia gas is: 1:4; the reaction pressure is 0.6Mpa, and the space velocity of the sebacic acid is 1h -1 ；
And S4, rectifying and purifying the crude product to obtain the product of the decanedionitrile.
The specific test results of examples 1-3 and comparative examples 1-6 are shown in Table 1:
TABLE 1
As can be seen from Table 1, the preparation method of decanedinitrile of the present invention has excellent yield, and the yield of the present invention can reach 99.1% by selecting the catalyst of the present invention and utilizing the interaction between the components.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such modifications are intended to be included in the scope of the present invention.
Claims (10)
1. A method for preparing decanedinitrile, which is characterized in that: the preparation method comprises the following steps:
s1, selecting ZnCuMg/Al 2 O 3 The mixture of the catalyst and phosphorus pentoxide is used as a catalyst bed layer;
s2, filling the catalyst bed layer prepared in the step S1 into a fixed bed reactor;
s3, metering by a sebacic acid feeder, entering a preheating section, preheating, and entering a catalyst bed layer together with ammonia gas for reaction;
and S4, rectifying and purifying the crude product to obtain the product of the decanedionitrile.
2. The process for preparing sebacic dinitrile according to claim 1, wherein: in the S1 step, znCuMg/Al 2 O 3 The mass ratio of the phosphorus pentoxide to the phosphorus pentoxide is 1; the molar ratio of zinc, copper, magnesium and aluminum is 1: 0.02-0.06.
3. The process for preparing sebacic dinitrile according to claim 1, wherein: in the step S3, the preheating temperature is 120-240 ℃, and the reaction conditions are as follows: the molar ratio of sebacic acid to ammonia gas is: 1:2 to 7; the reaction pressure is 0.1-1 Mpa, the space velocity of the sebacic acid is 0.4-1.2 h -1 。
4. The process for preparing sebacic dinitrile according to claim 1, wherein: the ZnCuMg/Al 2 O 3 The preparation method comprises the following steps:
dissolving zinc salt, copper salt and magnesium salt in deionized water to prepare a mixed solution, then slowly dropwise adding a precipitator into the mixed solution under the stirring condition, and controlling the pH value to be 9-10; aging and washing to obtain a precursor, and then mixing and pulping the precursor and aluminum hydroxide to obtain catalyst slurry; spray drying and calcining to obtain the product ZnCuMg/Al 2 O 3 。
5. The process for preparing sebacic dinitrile according to claim 4, wherein: the molar ratio of the zinc salt to the copper salt to the magnesium salt to the aluminum hydroxide is 1: 0.02-0.06.
6. The process for preparing decanedinitrile according to claim 4, wherein: the zinc salt is at least one of zinc nitrate, zinc acetate and zinc chloride; the copper salt is at least one of copper nitrate, copper acetate and copper chloride; the magnesium salt is at least one of magnesium nitrate, magnesium acetate and magnesium chloride.
7. The process for preparing decanedinitrile according to claim 4, wherein: the precipitator is at least one of sodium hydroxide solution, potassium hydroxide solution and sodium carbonate solution; the concentration of the precipitant is 2-4 mol/L.
8. The process for preparing sebacic dinitrile according to claim 4, wherein: the temperature in the precipitation process is 50-70 ℃; the aging time is 30-60 min.
9. The process for preparing sebacic dinitrile according to claim 4, wherein: the roasting conditions are as follows: roasting at 500-600 deg.c for 0.5-1.5 hr.
10. The process for preparing sebacic dinitrile according to claim 1, wherein: the ZnCuMg/Al 2 O 3 The mixture with phosphorus pentoxide is prepared by mixing ZnCuMg/Al 2 O 3 And stirring and mixing the mixture and phosphorus pentoxide at the mass ratio of 1: 0.2-0.4 to obtain a mixture.
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