CN111072490A - Method for preparing hexamethylene diamine from hexamethylene dialdehyde based on Ni-based catalyst - Google Patents
Method for preparing hexamethylene diamine from hexamethylene dialdehyde based on Ni-based catalyst Download PDFInfo
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- CN111072490A CN111072490A CN201911300260.XA CN201911300260A CN111072490A CN 111072490 A CN111072490 A CN 111072490A CN 201911300260 A CN201911300260 A CN 201911300260A CN 111072490 A CN111072490 A CN 111072490A
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- hydrotalcite
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- 239000003054 catalyst Substances 0.000 title claims abstract description 85
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 21
- -1 hexamethylene dialdehyde Chemical compound 0.000 title claims abstract description 8
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 43
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims abstract description 42
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 42
- UMHJEEQLYBKSAN-UHFFFAOYSA-N Adipaldehyde Chemical compound O=CCCCCC=O UMHJEEQLYBKSAN-UHFFFAOYSA-N 0.000 claims abstract description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052751 metal Inorganic materials 0.000 claims description 30
- 239000002184 metal Substances 0.000 claims description 30
- 239000011259 mixed solution Substances 0.000 claims description 25
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 24
- 150000001342 alkaline earth metals Chemical group 0.000 claims description 23
- 150000001768 cations Chemical class 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 238000002360 preparation method Methods 0.000 claims description 15
- 230000032683 aging Effects 0.000 claims description 11
- 238000011068 loading method Methods 0.000 claims description 6
- 229910021645 metal ion Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims 1
- 239000012716 precipitator Substances 0.000 claims 1
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 abstract description 8
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 abstract description 8
- 238000006268 reductive amination reaction Methods 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 3
- 231100000331 toxic Toxicity 0.000 abstract description 2
- 230000002588 toxic effect Effects 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 59
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 29
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 239000002243 precursor Substances 0.000 description 15
- 229910002651 NO3 Inorganic materials 0.000 description 13
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 13
- 239000006185 dispersion Substances 0.000 description 10
- 238000001035 drying Methods 0.000 description 8
- 229910003275 NiMgAl Inorganic materials 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 239000012153 distilled water Substances 0.000 description 7
- 230000007935 neutral effect Effects 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 239000000725 suspension Substances 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 229920002302 Nylon 6,6 Polymers 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- JBDIMNRIQHSXQD-UHFFFAOYSA-N [C].C(CCCCC=O)=O Chemical compound [C].C(CCCCC=O)=O JBDIMNRIQHSXQD-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- NZOHLEDRKVIKHS-UHFFFAOYSA-N NCCCCCCN.[C] Chemical compound NCCCCCCN.[C] NZOHLEDRKVIKHS-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 201000010041 presbyopia Diseases 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
Classifications
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- 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
- B01J23/78—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 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
- B01J23/70—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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/394—Metal dispersion value, e.g. percentage or fraction
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/24—Preparation of compounds containing amino groups bound to a carbon skeleton by reductive alkylation of ammonia, amines or compounds having groups reducible to amino groups, with carbonyl compounds
- C07C209/26—Preparation of compounds containing amino groups bound to a carbon skeleton by reductive alkylation of ammonia, amines or compounds having groups reducible to amino groups, with carbonyl compounds by reduction with hydrogen
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
The application discloses a method for preparing hexamethylene diamine from hexamethylene dialdehyde based on a Ni-based catalyst, which comprises the step of reacting a raw material containing the hexamethylene dialdehyde in the presence of ammonia gas, hydrogen gas and the Ni-based catalyst to generate the hexamethylene diamine, wherein the Ni-based catalyst is prepared from Ni-containing material2+And (3) preparing the hydrotalcite. The method adopts Ni-containing2+The hexanediamine is prepared by the catalytic adipaldehyde prepared from the hydrotalcite through reductive amination, so that the use of a highly toxic raw material adiponitrile is avoided, and the route is clean and environment-friendly.
Description
Technical Field
The application relates to a method for preparing hexamethylene diamine from hexamethylene dialdehyde based on a Ni-based catalyst, belonging to the field of chemical engineering.
Background
Hexamethylenediamine is an important organic chemical raw material, and can be used for preparing polyhexamethylene adipamide, also called polyamide 66(PA66) or nylon 66, by a polycondensation reaction with adipic acid. In recent years, the application field of hexamethylenediamine has been rapidly expanded. With the continuous development of the automobile industry in China, China gradually becomes the largest automobile manufacturing country in the world, under the trends of light weight, environmental protection and energy conservation, the demand of the automobile industry on nylon 66 also shows a rising trend, and nylon 66 faces a larger supply and demand gap.
The production of hexamethylene diamine is mainly monopolized by some large-scale transnational companies, the total of three members of Invida, Pasteur and Oshende accounts for 74% of the global productivity, the hexamethylene diamine is in the high oligopolistic industry, and the global productivity of China Mars, ranked on the fourth place, accounts for 9%.
CN109647419A discloses a method for preparing hexanediamine by using nickel-based catalyst loaded on alumina as active component and catalyzing adiponitrile hydrogenation in a tank reactor. US5900511 discloses a continuous adiponitrile hydrogenation process using Ni and Cr modified Raney Co catalyst to catalyze the hydrogenation of adiponitrile to produce hexamethylenediamine in a tank reactor.
From the literature and the technology which are available at present, the raw material adiponitrile in the industrialized adiponitrile hydrogenation preparation route of the hexamethylenediamine is high in toxicity, dependent on import and high in price. The development of a new green hexamethylenediamine preparation process is of great significance. Therefore, the development of a catalyst with good catalyst activity and target product selectivity is the key for realizing a green new process of the hexamethylene diamine.
Disclosure of Invention
According to one aspect of the present application, there is provided a process for the preparation of hexamethylenediamine from hexamethylenedialdehyde based on Ni-based catalyst, using a catalyst comprising Ni2+The catalyst prepared from the hydrotalcite is used for catalyzing adipic dialdehyde to prepare hexamethylene diamine through reductive amination, so that the use of a highly toxic raw material adiponitrile is avoided, and the route is clean and environment-friendly.
A method for preparing hexanediamine from hexanedialdehyde comprises adding raw material containing hexanedialdehyde into ammoniaGas, hydrogen and Ni-based catalyst to generate hexamethylene diamine, wherein the Ni-based catalyst contains Ni2+And (3) preparing the hydrotalcite.
Specifically, the Ni-containing alloy of the present invention2+The hydrotalcite is that divalent metal ions forming a layered structure of the hydrotalcite contain Ni2+；
The reaction conditions include:
the reaction temperature is 80-200 ℃;
the reaction pressure is 1-20 Mpa.
Optionally, the molar ratio of hydrogen to adipaldehyde is 5-60: 1.
optionally, the molar ratio of ammonia to adipaldehyde is 5-60: 1, preferably 10-60: 1.
Optionally, the divalent metal cations of the hydrotalcite further comprise Mg2+、Co2+、Zn2+Or Cu2+At least one of;
the trivalent metal cation of the hydrotalcite is selected from Al3+、Cr3+、Fe3+Or Sc3+At least one of (1).
The mass content of Ni in the Ni-based catalyst is 5-50%.
Optionally, the molar ratio of divalent metal cations to trivalent metal cations of the hydrotalcite is 2.5-3.5: 1, wherein Ni is2+The molar ratio of the metal ions to other divalent metal cations is 0.1-100: 1.
optionally, the Ni-based catalyst is an alkaline earth metal modified Ni-based catalyst.
Optionally, the alkaline earth metal comprises at least one of Mg, Ca, Sr, Ba;
the mass loading of the alkaline earth metal is 1.0-5.0%.
In the examples of the present invention, the alkaline earth metal mass loading was based on the total amount of the catalyst. Alternatively, the alkaline earth metal may be present in a mass loading with an upper limit selected from 5.0%, 4.0%, 3.0% or 2.0% and a lower limit selected from 4.0%, 3.0%, 2.0% or 1.0%.
Alternatively, the alkaline earth metal-modified Ni-based catalyst is obtained by:
adding the Ni-based catalyst into a salt solution containing alkaline earth metal, soaking in the same volume, and roasting to obtain the alkaline earth metal modified Ni-based catalyst.
Alternatively, the Ni-based catalyst consists of Ni2+The hydrotalcite is obtained by roasting.
Optionally, the preparation method of the alkaline earth metal modified Ni-based catalyst specifically includes:
(1) coprecipitating and aging a mixed solution I containing metal cations and a mixed solution II containing a precipitant to obtain Ni-based hydrotalcite (i.e. the Ni-containing hydrotalcite2+Hydrotalcite) to obtain a Ni-based catalyst; wherein the metal cation comprises a divalent metal cation comprising Ni and a trivalent metal cation2+。
(2) And adding the Ni-based catalyst into a salt solution containing alkaline earth metal, soaking in the same volume, and roasting to obtain the alkaline earth metal modified Ni-based catalyst.
Optionally, the divalent metal cation further comprises Mg2+、Co2+、Zn2+Or Cu2+At least one of;
the trivalent metal cation is selected from Al3+、Cr3+、Fe3+Or Sc3+At least one of; the molar ratio of divalent metal cations to trivalent metal cations of the hydrotalcite is 2.5-3.5: 1, and Ni2+The molar ratio of the metal ions to other divalent metal cations is 0.1-100: 1.
alternatively, Ni2+The upper limit of the molar ratio to the other divalent metal cation may be selected from 100:1, 10:1, 9:1, 8:1, 7:1, 6:1, 5:1, 4:1, 3:1, 2:1, 1:1 or 0.5:1, and the lower limit may be selected from 10:1, 9:1, 8:1, 7:1, 6:1, 5:1, 4:1, 3:1, 2:1, 1:1, 0.5:1 or 0.1: 1.
Optionally, the reaction conditions of the coprecipitation of step (1) include:
the temperature is 60-70 ℃;
the pH value is 8-12.
Optionally, the metal cation toAt least one selected from nitrate, sulfate, acetate and chloride of metal; the precipitant is Na2CO3At least one of NaOH and ammonia water.
Optionally, the aging conditions include:
the aging temperature is 60-70 ℃;
the time for presbyopia is 36-96 h.
Alternatively, the firing conditions after the Ni-based hydrotalcite is prepared include:
the temperature is 400-600 ℃;
the roasting time is 3-5 h.
Optionally, the reactor is selected from one of a fixed bed reactor, a trickle bed or a tank reactor.
The beneficial effects that this application can produce include:
1) by using a catalyst composed of Ni2+The catalyst prepared from the hydrotalcite is used for catalyzing adipic dialdehyde to prepare hexamethylene diamine through reductive amination, so that the use of a virulent raw material adiponitrile is avoided, and the route is clean and environment-friendly;
2) the catalyst is prepared by using a hydrotalcite precursor to obtain a high-dispersion Ni-based catalyst, so that the dispersion degree of Ni is effectively improved, the acidity and alkalinity of the catalyst are adjusted through alkaline earth metal modification, the prepared catalyst has the characteristics of metal catalysis and alkaline catalysis, and the catalyst can reduce the adsorption of amine when being applied to the reductive amination reaction of hexanedial, thereby reducing the occurrence of side reactions and showing good activity and selectivity; ni2+The catalyst is positioned in the layered structure of the catalyst, so that the loss of metal ions in the reaction process can be effectively reduced.
3) The catalyst provided by the invention has the advantages of simple preparation method, convenience in operation, low cost, reusability and potential economic benefit.
Detailed Description
The present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.
The raw materials in the examples of the present invention were all purchased from commercial sources unless otherwise specified.
The analytical methods and conversion, selectivity in the examples were calculated as follows:
analysis was performed using an Agilent7890 gas chromatograph with an autosampler. After the reaction is finished, adding n-octylamine into the reaction solution as an internal standard, and carrying out quantitative analysis by an internal standard method.
In some embodiments of the invention, both conversion and selectivity are calculated based on carbon moles:
conversion of adipaldehyde [ (adipaldehyde carbon mole number in feed) - (adipaldehyde carbon mole number in discharge) ]/(adipaldehyde carbon mole number in feed) × 100%
Hexamethylenediamine selectivity (the mole number of hexamethylenediamine carbon in the discharged material) ÷ (the total mole number of all carbon-containing products in the discharged material) × 100%
Hexamethylenediamine yield (moles of hexamethylenediamine carbon in the discharge) ÷ (moles of converted hexamethylenedialdehyde carbon) × 100%
The ion ratios in the examples are molar ratios unless otherwise specified.
EXAMPLE 1 preparation of NiMgAl-01 catalyst with hydrotalcite as precursor, (Ni)2++Mg2+)：Al3+The ratio of (A) to (B) is 3:1, Ni2+：Mg2+The ratio of (A) to (B) is 0.1.
9.52gNi(NO3)2·6H2O，46.89gAl(NO3)3·9H2O and 83.92gMg (NO)3)2·6H2Completely dissolving O in 500ml of water to obtain a mixed solution I; 26.5g Na were weighed2CO3And 70g of NaOH is completely dissolved in 1L of water to obtain a mixed solution II; and slowly dripping the two mixed solutions into 200mL of water at the same time, violently stirring, keeping the pH value at 10 at the rotation speed of 600r/min, transferring the obtained colloidal suspension into an oven after dripping is finished, aging for 72h at 65 ℃, cooling, washing with distilled water to be neutral, drying to obtain Ni-based hydrotalcite, and further roasting the obtained Ni-based hydrotalcite precursor for 4h at 500 ℃ to obtain the high-dispersion Ni-based catalyst.
Example 2 preparation of NiMgAl-02 catalyst with hydrotalcite as precursor, (Ni)2++Mg2+)：Al3+The ratio of (A) to (B) is 3:1, Ni2+：Mg2+The ratio of (A) to (B) is 1.0.
52.34gNi(NO3)2·6H2O，46.89gAl(NO3)3·9H2O and 46.15gMg (NO)3)2·6H2Completely dissolving O in 500ml of water to obtain a mixed solution I; 26.5g Na were weighed2CO3And 70g of NaOH is completely dissolved in 1L of water to obtain a mixed solution II; and slowly dripping the two mixed solutions into 200mL of water at the same time, violently stirring, keeping the pH value at 10 at the rotation speed of 600r/min, transferring the obtained colloidal suspension into an oven after dripping is finished, aging for 72h at 65 ℃, cooling, washing with distilled water to be neutral, drying to obtain Ni-based hydrotalcite, and further roasting the obtained Ni-based hydrotalcite precursor for 4h at 500 ℃ to obtain the high-dispersion Ni-based catalyst.
EXAMPLE 3 preparation of NiMgAl-03 catalyst with hydrotalcite as precursor, (Ni)2++Mg2+)：Al3+The ratio of (A) to (B) is 3:1, Ni2+：Mg2+Is 3.0
78.52gNi(NO3)2·6H2O，46.89gAl(NO3)3·9H2O and 23.07gMg (NO)3)2·6H2Completely dissolving O in 500ml of water to obtain a mixed solution I; 26.5g Na were weighed2CO3And 70g of NaOH is completely dissolved in 1L of water to obtain a mixed solution II; and slowly dripping the two mixed solutions into 200mL of water at the same time, violently stirring, keeping the pH value at 10 at the rotation speed of 600r/min, transferring the obtained colloidal suspension into an oven after dripping is finished, aging for 72h at 65 ℃, cooling, washing with distilled water to be neutral, drying to obtain Ni-based hydrotalcite, and further roasting the obtained Ni-based hydrotalcite precursor for 4h at 500 ℃ to obtain the high-dispersion Ni-based catalyst.
EXAMPLE 4 preparation of NiMgAl-04 catalyst from hydrotalcite precursor, (Ni)2++Mg2+)：Al3+The ratio of (A) to (B) is 3:1, Ni2+：Mg2+Has a ratio of 6.0
89.73gNi(NO3)2·6H2O，46.89gAl(NO3)3·9H2O and 13.18gMg (NO)3)2·6H2Completely dissolving O in 500ml of water to obtain a mixed solution I; 26.5g Na were weighed2CO3And 70g of NaOH is completely dissolved in 1L of water to obtain a mixed solution II; and slowly dripping the two mixed solutions into 200mL of water at the same time, violently stirring, keeping the pH value at 10 at the rotation speed of 600r/min, transferring the obtained colloidal suspension into an oven after dripping is finished, aging for 72h at 65 ℃, cooling, washing with distilled water to be neutral, drying to obtain Ni-based hydrotalcite, and further roasting the obtained Ni-based hydrotalcite precursor for 4h at 500 ℃ to obtain the high-dispersion Ni-based catalyst.
EXAMPLE 5 preparation of NiMgAl-05 catalyst with hydrotalcite as precursor, (Ni)2++Mg2+)：Al3+The ratio of (A) to (B) is 3:1, Ni2+：Mg2+Is 10.0
95.17gNi(NO3)2·6H2O，46.89gAl(NO3)3·9H2O and 8.39gMg (NO)3)2·6H2Completely dissolving O in 500ml of water to obtain a mixed solution I; 26.5g Na were weighed2CO3And 70g NaOH is completely dissolved in 1L of water to obtain a mixed solution II; and slowly dripping the two mixed solutions into 200mL of water at the same time, violently stirring, keeping the pH value at 10 at the rotation speed of 600r/min, transferring the obtained colloidal suspension into an oven after dripping is finished, aging for 72h at 65 ℃, cooling, washing with distilled water to be neutral, drying to obtain Ni-based hydrotalcite, and further roasting the obtained Ni-based hydrotalcite precursor for 4h at 500 ℃ to obtain the high-dispersion Ni-based catalyst.
EXAMPLE 6 preparation of NiZnAl-01 catalyst with hydrotalcite as precursor, (Ni)2++Zn2+)：Al3+The ratio of (A) to (B) is 2:1, Ni2+：Zn2+The ratio of (1): 1
36.34gNi(NO3)2·6H2O，40.39gAl(NO3)3·9H2O and 37.19gZn (NO)3)2·6H2Completely dissolving O in 500ml of water to obtain a mixed solution I; 26.5g Na were weighed2CO3And 70g NaOH is completely dissolved in 1L of water to obtain a mixed solution II; slowly adding the two mixed solutions into 200mL of water at the same time, stirring vigorously at a rotation speed of 600r/min, maintaining pH at 10, and transferring the obtained colloidal suspension to a reactorAnd (3) putting the catalyst into an oven, aging for 72h at 65 ℃, cooling, washing with distilled water to be neutral, drying to obtain Ni-based hydrotalcite, and further roasting the obtained Ni-based hydrotalcite precursor for 4h at 500 ℃ to obtain the high-dispersion Ni-based catalyst.
EXAMPLE 7 preparation of NiCoFe-01 catalyst with hydrotalcite as precursor, (Ni)2++Co2+)：Fe3+The ratio of (1): 1, Ni2+：Co2+The ratio of (A) to (B) is 3:1
21.8g Ni(NO3)2·6H2O，40.39g Fe(NO3)3·9H2O and 7.27g Co (NO)3)2·6H2Completely dissolving O in 500ml of water to obtain a mixed solution I; 26.5g Na were weighed2CO3And 70g NaOH is completely dissolved in 1L of water to obtain a mixed solution II; and slowly dripping the two mixed solutions into 200mL of water at the same time, violently stirring, keeping the pH value at 10 at the rotation speed of 600r/min, transferring the obtained colloidal suspension into an oven after dripping is finished, aging for 72h at 65 ℃, cooling, washing with distilled water to be neutral, drying to obtain Ni-based hydrotalcite, and further roasting the obtained Ni-based hydrotalcite precursor for 4h at 500 ℃ to obtain the high-dispersion Ni-based catalyst.
Example 8 alkaline earth metal modified NiMgAl catalyst
0.89gMg (CH)3COO)2·4H2Dissolving O in water, metering to 15mL, taking 10g of NiMgAl-03 catalyst (namely the high-dispersion Ni-based catalyst provided in the embodiment 3), loading Mg element on the NiMgAl catalyst by adopting an isometric impregnation method, placing the NiMgAl catalyst in a 100 ℃ oven for drying for 12h, and then roasting the NiMgAl catalyst in a 500 ℃ muffle furnace for 4h to obtain the alkaline earth metal modified NiMgAl catalyst which is marked as 1.0 Mg/NiMgAl-03.
Examples 9 to 18 alkaline earth metal-modified Ni-based catalysts
The method provided in example 8 was used to prepare the alkaline earth metal modified catalyst by replacing the catalyst (i.e., the highly dispersed Ni-based catalyst provided in examples 1 to 7), the type and content of the alkaline earth metal salt, and the specific preparation conditions are shown in table 1.
TABLE 1 preparation parameters for catalysts in examples 8-18
In the catalysts nA/B, n represents a metal loading amount, A represents a loaded metal, and B represents a NiMgAl catalyst (provided in examples 1 to 5).
EXAMPLES 19-30 evaluation of reactivity of catalysts
Filling 2.0g of the catalyst into a stainless steel fixed bed reactor with the inner diameter of 10mm and the length of 300mm, filling quartz sand at two ends of the catalyst, firstly introducing reducing gas at the flow rate of 30mL/min, and reducing the catalyst for 4 hours at the temperature of 400 ℃, wherein the reducing gas is H2/N21/4 by volume ratio.
After the reduction is finished, the temperature of the reactor is reduced to the reaction temperature, the reactor is pressurized to the reaction pressure, and H is respectively introduced into the reactor2Liquid ammonia and hexanedial are subjected to reductive amination reaction, wherein the liquid ammonia and the hexanedial are respectively injected into the reactor through a high-pressure trace feed pump, and the mass space velocity of the hexanedial is 1.0h-1And sampling for analysis after 10h of reaction, and the reaction results are shown in Table 2.
Table 2 reactivity of catalysts prepared in example 3, examples 8-18
As can be seen from Table 2, the catalyst provided by each embodiment of the invention has excellent selectivity on hexamethylene diamine in the reaction of preparing hexanediamine by reductive amination of hexanediamine, wherein the selectivity of the hexanediamine can reach 87.3 percent at most, and the conversion rate of the hexanediamine can reach 99.7 percent at most; example 19 shows a NiMgAl catalyst that is not modified with an alkaline earth metal, where the selectivity of hexamethylenediamine in the reaction of reductive amination of hexanedial to produce hexanediamine is only 35.4%, which is much lower than that of the catalyst modified with an alkaline earth metal, and further demonstrates that the catalyst prepared by modifying with an alkaline earth metal to adjust the acidity or basicity of the catalyst has both the characteristics of metal catalysis and basic catalysis, and shows good activity and selectivity when applied to the reductive amination of hexanedial.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (10)
1. The method for preparing hexamethylene diamine from hexamethylene dialdehyde is characterized in that raw materials containing the hexamethylene dialdehyde react in the presence of ammonia gas, hydrogen gas and a Ni-based catalyst to generate the hexamethylene diamine, wherein the Ni-based catalyst is prepared from Ni2+And (3) preparing the hydrotalcite.
2. The method of claim 1, wherein the reaction conditions comprise:
the reaction temperature is 80-200 ℃;
the reaction pressure is 1-20 Mpa.
3. The method according to claim 1, wherein the molar ratio of hydrogen to adipaldehyde is 5-60: 1, the molar ratio of ammonia to adipaldehyde is 5-60: 1.
4. the process according to claim 1, characterized in that the divalent metal cations of the hydrotalcite further comprise Mg2+、Co2+、Zn2+Or Cu2+At least one of;
the trivalent metal cation of the hydrotalcite is selected from Al3+、Cr3+、Fe3+Or Sc3+At least one of (1).
5. The method of claim 4, wherein: the mass content of Ni in the Ni-based catalyst is 5-50%.
6. The method of claim 1, whichIs characterized in that: the molar ratio of divalent metal cations to trivalent metal cations of the hydrotalcite is 1.0-4.0: 1, wherein Ni2+The molar ratio of the metal ions to other divalent metal cations is 0.1-100: 1.
7. the method of claim 1, wherein: the Ni-based catalyst is an alkaline earth metal modified Ni-based catalyst.
8. The method of claim 7, wherein: the alkaline earth metal comprises at least one of Mg, Ca, Sr and Ba;
the mass loading of the alkaline earth metal is 1.0-5.0%.
9. The method according to claim 7, characterized in that the alkaline earth metal modified Ni based catalyst is obtained by:
adding the Ni-based catalyst into a salt solution containing alkaline earth metal, soaking in the same volume, and roasting to obtain the alkaline earth metal modified Ni-based catalyst.
10. The method according to claim 9, wherein the Ni-based catalyst preparation method comprises:
coprecipitating the mixed solution I containing metal cations and the mixed solution II containing a precipitator, and aging to obtain the Ni-containing alloy2+Calcining the hydrotalcite to obtain the Ni-based catalyst; wherein the metal cation comprises a divalent metal cation comprising Ni and a trivalent metal cation2+。
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