CN112920056B - Method for producing isopropanolamine and 1, 2-propanediamine by cracking 2, 5-dimethylpiperazine - Google Patents
Method for producing isopropanolamine and 1, 2-propanediamine by cracking 2, 5-dimethylpiperazine Download PDFInfo
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- NSMWYRLQHIXVAP-UHFFFAOYSA-N 2,5-dimethylpiperazine Chemical compound CC1CNC(C)CN1 NSMWYRLQHIXVAP-UHFFFAOYSA-N 0.000 title claims abstract description 53
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 229940102253 isopropanolamine Drugs 0.000 title claims abstract description 52
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000005336 cracking Methods 0.000 title claims abstract description 36
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 74
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 29
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 238000004821 distillation Methods 0.000 claims abstract description 11
- 238000000926 separation method Methods 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- 238000001035 drying Methods 0.000 claims description 40
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 29
- 238000005470 impregnation Methods 0.000 claims description 21
- 239000012018 catalyst precursor Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 17
- 230000032683 aging Effects 0.000 claims description 15
- 238000002791 soaking Methods 0.000 claims description 13
- 229910021529 ammonia Inorganic materials 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims description 10
- 239000006200 vaporizer Substances 0.000 claims description 9
- 229910044991 metal oxide Inorganic materials 0.000 claims description 8
- 150000004706 metal oxides Chemical class 0.000 claims description 8
- 238000003776 cleavage reaction Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000006386 neutralization reaction Methods 0.000 claims description 6
- 230000007017 scission Effects 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 5
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 5
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 5
- WFLYOQCSIHENTM-UHFFFAOYSA-N molybdenum(4+) tetranitrate Chemical compound [N+](=O)([O-])[O-].[Mo+4].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] WFLYOQCSIHENTM-UHFFFAOYSA-N 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 238000005096 rolling process Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- 230000003472 neutralizing effect Effects 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 13
- 229910018626 Al(OH) Inorganic materials 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000001514 detection method Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 4
- -1 organic synthesis Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000003507 refrigerant Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910020630 Co Ni Inorganic materials 0.000 description 2
- 229910002440 Co–Ni Inorganic materials 0.000 description 2
- 229910020708 Co—Pd Inorganic materials 0.000 description 2
- 229910017318 Mo—Ni Inorganic materials 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910003296 Ni-Mo Inorganic materials 0.000 description 1
- 229920002334 Spandex Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000001093 anti-cancer Effects 0.000 description 1
- 239000013556 antirust agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 239000010730 cutting oil Substances 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N dimethylmethane Natural products CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- ZLGIYFNHBLSMPS-ATJNOEHPSA-N shellac Chemical class OCCCCCC(O)C(O)CCCCCCCC(O)=O.C1C23[C@H](C(O)=O)CCC2[C@](C)(CO)[C@@H]1C(C(O)=O)=C[C@@H]3O ZLGIYFNHBLSMPS-ATJNOEHPSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004759 spandex Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/62—Preparation of compounds containing amino groups bound to a carbon skeleton by cleaving carbon-to-nitrogen, sulfur-to-nitrogen, or phosphorus-to-nitrogen bonds, e.g. hydrolysis of amides, N-dealkylation of amines or quaternary ammonium compounds
-
- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/892—Nickel and noble metals
-
- B01J35/615—
-
- B01J35/633—
-
- B01J35/635—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
Abstract
The invention belongs to the technical field of organic synthesis, and particularly relates to a method for producing isopropanolamine and 1, 2-propane diamine by cracking 2, 5-dimethylpiperazine. 2, 5-dimethylpiperazine in Co-Ni-Pd/Al 2 O 3 Under the action of a catalyst, a contact cracking reaction is carried out to prepare a mixture of isopropanolamine and 1, 2-propane diamine, and pure isopropanolamine and 1, 2-propane diamine are obtained by distillation and separation. The method for producing isopropanolamine and 1, 2-propane diamine by cracking 2, 5-dimethylpiperazine adopts Co-Ni-Pd/Al 2 O 3 The catalyst has the advantages of high specific surface area, high mechanical strength, good stability, simple preparation process and high catalytic activity on cracking 2, 5-dimethyl piperazine.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a method for producing isopropanolamine and 1, 2-propane diamine by cracking 2, 5-dimethylpiperazine.
Background
The 1, 2-propane diamine is an organic chemical intermediate and a raw material with wide application, has important application in the fields of medicines, pesticides, organic synthesis, lubricating oil antirust agents, epoxy resin curing accelerators, spandex and modified shellac coatings and the like, and can be used as rubber, coatings, raw materials, chelating agents, mineral dressing agents and the like, and can be used for producing 1, 2-propane diamine tetraacetic acid as an intermediate of anticancer medicine propane imine.
Because the isopropanolamine has less harm to the environment and human body, the isopropanolamine becomes a green chemical product which is strongly advocated and encouraged in developed countries. Isopropanolamine is used for the synthesis of textile auxiliaries (finishing agents, antistatic agents, dyeing auxiliaries, penetrants), emulsifiers (for cutting oils, coatings, insecticides), polishes, tanning agents, plasticizers, etc.; also used as a non-aqueous catalyst for the pre-reaction of solvent-type chloroprene adhesive 2402 resin and active magnesium oxide. At the same time, isopropanolamine is also one of the important raw materials for preparing 1, 2-propanediamine.
Patent CN 201110449743.3 discloses a process for producing 1, 2-propane diamine, which comprises adding isopropanolamine and catalyst into a 1-liter pressure reaction kettle, and replacing air in the pressure reaction kettle with nitrogen for three times; then adding ammonia, wherein the molar ratio of isopropanolamine to ammonia is 1.2-1.3, and heating to 150-155 ℃ under stirring; introducing hydrogen to make the pressure reach 8-12MPa, and keeping the pressure with the hydrogen to react for 4-5 hours; after the reaction is finished, cooling the reaction solution to room temperature, emptying, and removing hydrogen in the reaction kettle by using nitrogen; filtering the reaction liquid to recover the catalyst, and rectifying the filtrate at normal pressure to obtain a finished product of the 1, 2-propane diamine; the catalyst is a mixture of NiO, coO and CuO, and the catalyst carrier is Al 2 O 3 The weight percentage of the catalyst is NiO10%, coO10% and CuO5%, and the dosage of the catalyst is 2-3% of the weight of the isopropanolamine.
In the above reaction process, isopropanolamine as a raw material is combined with 1, 2-propanediamine as a product to produce a large amount of 2, 5-dimethylpiperazine as a by-product, which affects the yield, and 2, 5-dimethylpiperazine as a by-product has a low price and is not economical.
Patent CN111925341A discloses a method for preparing piperazine by using diethanolamine in Co-Ni-Mo/Al 2 O 3 And (3) carrying out continuous gas-solid reaction under the action of a catalyst to prepare the piperazine. However, such catalysts have not been demonstrated in the laboratory for the cleavage of 2, 5-dimethylpiperazine.
How to reuse the 2, 5-dimethylpiperazine as a byproduct becomes a hotspot and a difficulty for research of researchers.
Disclosure of Invention
The purpose of the invention is: providing a method for producing isopropanolamine and 1, 2-propane diamine by cracking 2, 5-dimethylpiperazine; the method improves the economic value of the 2, 5-dimethylpiperazine, the reaction conditions are easy to control, and the prepared isopropanolamine and 1, 2-propane diamine have high purity and yield.
The invention relates to a method for producing isopropanolamine and 1, 2-propane diamine by cracking 2, 5-dimethylpiperazine, in the presence of Co-Ni-Pd/Al of 2, 5-dimethylpiperazine 2 O 3 Under the action of catalyst, the mixture of isopropanolamine and 1, 2-propane diamine is obtained through contact cracking reactionThen pure isopropanolamine and 1, 2-propane diamine are obtained by distillation separation.
The Co-Ni-Pd/Al 2 O 3 The catalyst comprises, by weight of metal oxide, coO accounting for 1-3% of the weight of the catalyst, niO accounting for 1-3% of the weight of the catalyst, and PdO accounting for 1-4% of the weight of the catalyst.
The Co-Ni-Pd/Al 2 O 3 The pore volume of (A) is 0.4-0.6ml/g, the specific surface area is 250-350m 2 /g。
Preferably, the method for producing isopropanolamine and 1, 2-propanediamine by cracking 2, 5-dimethylpiperazine comprises the following steps:
(1) Introducing 2, 5-dimethyl piperazine into a vaporizer of a reaction system, heating and gasifying the mixture of ammonia and water, and reacting the mixture with Co-Ni-Pd/Al in the reactor 2 O 3 Carrying out contact cracking reaction on the catalyst;
(2) And (2) condensing the product obtained in the step (1), and then feeding the product into a distillation separation system to obtain pure isopropanolamine and 1, 2-propane diamine.
Wherein:
the temperature of the mixed gas of ammonia and water in the step (1) is 300-400 ℃.
The volume ratio of the ammonia gas to the water vapor in the step (1) is 1.
The pressure of the contact cracking reaction in the step (1) is 15-20 atmospheric pressures, and the reaction time is 40-70min.
And the unreacted 2, 5-dimethylpiperazine enters a vaporizer to participate in the next circulation.
And (3) the steam in the step (2) enters a condenser, is condensed to 50-70 ℃, and enters a distillation separation system, and the refrigerant is water.
The Co-Ni-Pd/Al 2 O 3 The preparation method of the catalyst comprises the following steps:
(1) Adding a sodium hydroxide solution into aluminum hydroxide, uniformly mixing, adding nitric acid for neutralization, then aging, filtering, washing, rolling ball molding, drying and roasting to prepare a spherical alumina carrier with the diameter of 3-5 mm;
(2) Mixing nitrate solutions of Co, ni and Pd according to a specific ratio to prepare a catalyst impregnation solution, pre-impregnating an alumina carrier to obtain a wet-bulb carrier, drying and roasting;
(3) Cooling the catalyst precursor prepared in the step (2), soaking the catalyst precursor in the catalyst soaking solution prepared in the step (2), taking out the catalyst precursor, drying and roasting the catalyst precursor to obtain Co-Ni-Pd/Al 2 O 3 A catalyst.
Wherein:
the reaction equation involved in step (1) is:
NaOH+Al(OH) 3 ＝NaAlO 2 +H 2 O
NaAlO 2 +H 2 O+HNO 3 ＝Al(OH) 3 ↓+NaNO 3 。
and (2) adding a sodium hydroxide solution in the step (1), mixing for 2-4h, and adding nitric acid for neutralization for 20-50min.
The aging temperature in the step (1) is 60-90 ℃, and the aging time is 4-6h; and then washed with water.
The drying temperature in the step (1) is 90-130 ℃, and the drying time is 4-6h; the roasting temperature is 250-450 ℃, and the roasting time is 2-3h.
The mass fraction of the cobalt nitrate solution in the step (2) is 10-30%; the mass fraction of the molybdenum nitrate solution is 10-30%; the mass fraction of the palladium nitrate solution is 10-30%.
The pre-impregnation time in the step (2) is 2-3h.
And (4) cooling to 30-50 ℃ in the step (3), and soaking again for 2-3h.
And (3) adopting equal-volume impregnation when impregnating in the impregnation solution in the step (2) and the impregnation solution in the step (3).
The drying and roasting process parameters in the step (2) and the step (3) are the same, the drying temperature is 90-130 ℃, and the drying time is 2-6h; the roasting temperature is 250-450 ℃, and the roasting time is 2-3h.
The method for producing isopropanolamine and 1, 2-propane diamine by cracking 2, 5-dimethylpiperazine relates to the reaction equation:
compared with the prior art, the invention has the following beneficial effects:
(1) The method for producing isopropanolamine and 1, 2-propane diamine by cracking 2, 5-dimethyl piperazine adopts Co-Ni-Pd/Al 2 O 3 The catalyst has the advantages of high specific surface area, high mechanical strength, good stability, simple preparation process and high catalytic activity on cracking 2, 5-dimethyl piperazine.
(2) The method for producing isopropanolamine and 1, 2-propane diamine by cracking 2, 5-dimethylpiperazine catalytically cracks 2, 5-dimethylpiperazine without economic value into isopropanolamine and 1, 2-propane diamine, widens the application range of 2, 5-dimethylpiperazine, and has the advantages of simple cracking process, easily controlled parameters and easy realization of industrial popularization.
Detailed Description
The present invention is further described below with reference to examples.
Example 1
The method for producing isopropanolamine and 1, 2-propanediamine by cracking 2, 5-dimethylpiperazine, described in example 1, consists of the following steps:
(1) Introducing 2, 5-dimethylpiperazine into a vaporizer of a reaction system, heating and gasifying the mixture gas of ammonia and water, and then mixing the mixture gas with Co-Ni-Pd/Al in the reactor 2 O 3 Carrying out contact cracking reaction on the catalyst;
(2) And (2) condensing the product obtained in the step (1), and then feeding the product into a distillation separation system to obtain pure isopropanolamine and 1, 2-propane diamine.
Wherein:
the Co-Ni-Pd/Al 2 O 3 The catalyst comprises 2% of CoO, 2% of NiO and 4% of PdO by weight, wherein CoO is 2% of the weight of the catalyst, niO is 2% of the weight of the catalyst and PdO is 4% of the weight of the catalyst.
The Co-Ni-Pd/Al 2 O 3 Has a pore volume of 0.5ml/g and a specific surface area of 290m 2 /g。
The temperature of the mixed gas of ammonia and water in the step (1) is 300 ℃.
The volume ratio of the ammonia gas to the water vapor in the step (1) is 1.
The pressure of the contact cracking reaction in the step (1) is 15 atmospheric pressures, and the reaction time is 50min.
And the unreacted 2, 5-dimethylpiperazine enters a vaporizer to participate in the next circulation.
And (3) feeding the steam in the step (2) into a condenser, condensing to 70 ℃, and feeding into a distillation separation system, wherein the refrigerant is water.
The Co-Ni-Pd/Al 2 O 3 The preparation method of the catalyst comprises the following steps:
(1) Adding a sodium hydroxide solution into aluminum hydroxide, uniformly mixing, adding nitric acid for neutralization, then aging, filtering, washing, rolling ball molding, drying and roasting to prepare a spherical alumina carrier with the diameter of 5 mm;
(2) Mixing nitrate solutions of Co, ni and Pd according to a specific ratio to prepare a catalyst impregnation liquid, pre-impregnating an alumina carrier to obtain a wet-ball carrier, drying and roasting;
(3) Cooling the catalyst precursor prepared in the step (2), soaking the catalyst precursor in the catalyst soaking solution prepared in the step (2), taking out the catalyst precursor, drying and roasting the catalyst precursor to obtain Co-Ni-Pd/Al 2 O 3 A catalyst.
Wherein:
the reaction equation involved in step (1) is:
NaOH+Al(OH) 3 ＝NaAlO 2 +H 2 O
NaAlO 2 +H 2 O+HNO 3 ＝Al(OH) 3 ↓+NaNO 3 。
and (2) adding a sodium hydroxide solution in the step (1), mixing for 2h, and adding nitric acid to neutralize for 25min.
The aging temperature in the step (1) is 75 ℃, and the aging time is 5 hours; and then washed with water.
The drying temperature in the step (1) is 110 ℃, and the drying time is 5h; the roasting temperature is 300 ℃, and the roasting time is 2.5h.
The mass fraction of the cobalt nitrate solution in the step (2) is 10%; the mass fraction of the molybdenum nitrate solution is 10 percent; the mass fraction of the palladium nitrate solution is 20%.
The pre-impregnation time in step (2) was 2.5h.
And (4) cooling to 30 ℃ in the step (3), and impregnating again, wherein the impregnating time is 2.5h.
And (4) adopting equal-volume impregnation when impregnating with the impregnation solution in the step (2) and the step (3).
The drying and roasting process parameters in the step (2) and the step (3) are the same, the drying temperature is 130 ℃, and the drying time is 5 hours; the roasting temperature is 350 ℃, and the roasting time is 2.5h.
The detection proves that the isopropanolamine accounts for 48.61 percent, the 1, 2-propane diamine accounts for 48.65 percent, the water accounts for 2.47 percent, and the 2, 5-dimethyl piperazine accounts for 0.27 percent in the product.
Example 2
The method for producing isopropanolamine and 1, 2-propanediamine by cracking 2, 5-dimethylpiperazine, described in example 2, consists of the following steps:
(1) Introducing 2, 5-dimethyl piperazine into a vaporizer of a reaction system, heating and gasifying the mixture of ammonia and water, and reacting the mixture with Co-Ni-Pd/Al in the reactor 2 O 3 The catalyst is subjected to contact cracking reaction;
(2) And (2) condensing the product obtained in the step (1), and then feeding the product into a distillation separation system to obtain pure isopropanolamine and 1, 2-propane diamine.
Wherein:
the Co-Ni-Pd/Al 2 O 3 The catalyst comprises 1% of CoO, 1% of NiO and 3% of PdO by weight, wherein CoO, niO and PdO are respectively calculated according to the weight of metal oxides.
The Co-Ni-Pd/Al 2 O 3 Has a pore volume of 0.6ml/g and a specific surface area of 320m 2 /g。
The temperature of the mixed gas of ammonia and water in the step (1) is 350 ℃.
The volume ratio of the ammonia gas to the water vapor in the step (1) is 1.
The pressure of the contact cracking reaction in the step (1) is 18 atmospheric pressures, and the reaction time is 60min.
And the unreacted 2, 5-dimethylpiperazine enters a vaporizer to participate in the next circulation.
And (3) feeding the steam in the step (2) into a condenser, condensing to 70 ℃, and feeding into a distillation separation system, wherein the refrigerant is water.
The Co-Ni-Pd/Al 2 O 3 The preparation method of the catalyst comprises the following steps:
(1) Adding a sodium hydroxide solution into aluminum hydroxide, uniformly mixing, adding nitric acid for neutralization, then aging, filtering, washing, rolling ball molding, drying and roasting to prepare a spherical alumina carrier with the diameter of 5 mm;
(2) Mixing nitrate solutions of Co, ni and Pd according to a specific ratio to prepare a catalyst impregnation solution, pre-impregnating an alumina carrier to obtain a wet-bulb carrier, drying and roasting;
(3) Cooling the catalyst precursor prepared in the step (2), soaking the catalyst precursor in the catalyst soaking solution prepared in the step (2), taking out the catalyst precursor, drying and roasting the catalyst precursor to obtain Co-Ni-Pd/Al 2 O 3 A catalyst.
Wherein:
the reaction equation involved in step (1) is:
NaOH+Al(OH) 3 ＝NaAlO 2 +H 2 O
NaAlO 2 +H 2 O+HNO 3 ＝Al(OH) 3 ↓+NaNO 3 。
and (2) adding a sodium hydroxide solution in the step (1), mixing for 3h, and adding nitric acid to neutralize for 40min.
The aging temperature in the step (1) is 80 ℃, and the aging time is 4h; and then washed with water.
The drying temperature in the step (1) is 120 ℃, and the drying time is 4.5h; the roasting temperature is 350 ℃, and the roasting time is 3h.
The mass fraction of the cobalt nitrate solution in the step (2) is 10%; the mass fraction of the molybdenum nitrate solution is 10 percent; the mass fraction of the palladium nitrate solution is 30%.
The pre-soaking time in the step (2) is 3h.
And (4) cooling to 40 ℃ in the step (3), and impregnating again for 3h.
And (3) adopting equal-volume impregnation when impregnating in the impregnation solution in the step (2) and the impregnation solution in the step (3).
The drying and roasting process parameters in the step (2) and the step (3) are the same, the drying temperature is 130 ℃, and the drying time is 5 hours; the roasting temperature is 380 ℃, and the roasting time is 3h.
The detection shows that the isopropanolamine accounts for 48.53 percent, the 1, 2-propane diamine accounts for 48.31 percent, the water accounts for 1.05 percent, and the 2, 5-dimethyl piperazine accounts for 2.11 percent.
Example 3
The method for producing isopropanolamine and 1, 2-propanediamine by cracking 2, 5-dimethylpiperazine, described in example 3, consists of the following steps:
(1) Introducing 2, 5-dimethyl piperazine into a vaporizer of a reaction system, heating and gasifying the mixture of ammonia and water, and reacting the mixture with Co-Ni-Pd/Al in the reactor 2 O 3 Carrying out contact cracking reaction on the catalyst;
(2) And (2) condensing the product obtained in the step (1), and then feeding the product into a distillation separation system to obtain pure isopropanolamine and 1, 2-propane diamine.
Wherein:
the Co-Ni-Pd/Al 2 O 3 The catalyst comprises, by weight of metal oxides, coO accounting for 3% of the weight of the catalyst, niO accounting for 3% of the weight of the catalyst, and PdO accounting for 4% of the weight of the catalyst.
The Co-Ni-Pd/Al 2 O 3 Has a pore volume of 0.4ml/g and a specific surface area of 250m 2 /g。
The temperature of the mixed gas of ammonia and water in the step (1) is 400 ℃.
The volume ratio of the ammonia gas to the water vapor in the step (1) is 1.
The pressure of the contact cracking reaction in the step (1) is 20 atmospheric pressures, and the reaction time is 40min.
And the unreacted 2, 5-dimethylpiperazine enters a vaporizer to participate in the next circulation.
And (3) feeding the steam in the step (2) into a condenser, condensing the steam to 70 ℃, and feeding the steam into a distillation separation system, wherein the refrigerant is water.
The Co-Ni-Pd/Al 2 O 3 The preparation method of the catalyst comprises the following steps:
(1) Adding a sodium hydroxide solution into aluminum hydroxide, uniformly mixing, adding nitric acid for neutralization, then aging, filtering, washing, rolling ball molding, drying and roasting to prepare a spherical alumina carrier with the diameter of 5 mm;
(2) Mixing nitrate solutions of Co, ni and Pd according to a specific ratio to prepare a catalyst impregnation liquid, pre-impregnating an alumina carrier to obtain a wet-ball carrier, drying and roasting;
(3) Cooling the catalyst precursor prepared in the step (2), soaking the catalyst precursor in the catalyst soaking solution prepared in the step (2), taking out the catalyst precursor, drying and roasting the catalyst precursor to obtain Co-Ni-Pd/Al 2 O 3 A catalyst.
Wherein:
the reaction equation involved in step (1) is:
NaOH+Al(OH) 3 ＝NaAlO 2 +H 2 O
NaAlO 2 +H 2 O+HNO 3 ＝Al(OH) 3 ↓+NaNO 3 。
and (2) adding a sodium hydroxide solution in the step (1), mixing for 3h, and adding nitric acid to neutralize for 50min.
The aging temperature in the step (1) is 90 ℃, and the aging time is 4h; and then washed with water.
The drying temperature in the step (1) is 130 ℃, and the drying time is 4h; the roasting temperature is 450 ℃, and the roasting time is 2 hours.
The mass fraction of the cobalt nitrate solution in the step (2) is 20%; the mass fraction of the molybdenum nitrate solution is 20 percent; the mass fraction of the palladium nitrate solution is 30%.
The pre-impregnation time in the step (2) is 3h.
And (4) cooling to 50 ℃ in the step (3), and impregnating again for 3h.
And (4) adopting equal-volume impregnation when impregnating with the impregnation solution in the step (2) and the step (3).
The drying and roasting process parameters in the step (2) and the step (3) are the same, the drying temperature is 130 ℃, and the drying time is 5 hours; the roasting temperature is 450 ℃, and the roasting time is 3 hours.
The detection shows that the isopropanolamine accounts for 47.39%, the 1, 2-propane diamine accounts for 47.14%, the water accounts for 2.23%, and the 2, 5-dimethyl piperazine accounts for 3.24%.
Comparative example 1
The method for producing isopropanolamine and 1, 2-propanediamine by cracking 2, 5-dimethylpiperazine in the comparative example 1 has the same process parameters as the method in the example 1, and has the only difference that the adopted catalyst is different, and Co-Ni/Al is adopted 2 O 3 Catalyst, said Co-Ni/Al 2 O 3 Catalyst, coO is 2% of catalyst weight and NiO is 2% of catalyst weight according to metal oxide weight.
Through detection, the isopropanolamine accounts for 38.34%, the 1, 2-propane diamine accounts for 38.20%, the water accounts for 3.11%, and the 2, 5-dimethyl piperazine accounts for 20.35% of the product.
Comparative example 2
The method for producing isopropanolamine and 1, 2-propanediamine by cracking 2, 5-dimethylpiperazine, which is described in comparative example 2, has the same process parameters as in example 1, and has the only difference that Co-Pd/Al is used as the catalyst 2 O 3 Catalyst, said Co-Pd/Al 2 O 3 Catalyst, coO is 2% of the catalyst weight and PdO is 2% of the catalyst weight based on the weight of the metal oxide.
The detection shows that the isopropanolamine accounts for 32.65%, the 1, 2-propane diamine accounts for 32.35%, the water accounts for 4.42%, and the 2, 5-dimethyl piperazine accounts for 30.58%.
Comparative example 3
The method for producing isopropanolamine and 1, 2-propanediamine by cracking 2, 5-dimethylpiperazine, which is described in the comparative example 3, has the same process parameters as those of the example 1, and has the only difference that the catalyst is different and Ni-Pd/Al is adopted 2 O 3 Catalyst, said Ni-Pd/Al 2 O 3 The catalyst comprises NiO accounting for 2 percent of the weight of the catalyst and PdO accounting for 2 percent of the weight of the catalyst according to the weight of metal oxides.
The detection shows that the isopropanolamine accounts for 29.29 percent, the 1, 2-propane diamine accounts for 28.89 percent, the water accounts for 3.59 percent, and the 2, 5-dimethyl piperazine accounts for 38.23 percent.
Comparative example 4
The method for producing isopropanolamine and 1, 2-propanediamine by cracking 2, 5-dimethylpiperazine, which is described in comparative example 4, has the same process parameters as in example 1, except that a catalyst different from Co-Mo-Ni/Al is used 2 O 3 Catalyst, said Co-Mo-Ni/Al 2 O 3 The catalyst comprises, by weight of metal oxides, 10% of CoO, 20% of NiO and 1.0% of MoO by weight of the catalyst.
The detection shows that the isopropanolamine accounts for 3.45 percent, the 1, 2-propane diamine accounts for 3.24 percent, the water accounts for 2.11 percent, and the 2, 5-dimethyl piperazine accounts for 91.20 percent.
Claims (8)
1. A method for producing isopropanolamine and 1, 2-propane diamine by cracking 2, 5-dimethylpiperazine is characterized in that: the method comprises the following steps:
(1) Introducing 2, 5-dimethylpiperazine into a vaporizer of a reaction system, heating and gasifying the mixture gas of ammonia and water, and then mixing the mixture gas with Co-Ni-Pd/Al in the reactor 2 O 3 The catalyst is subjected to contact cracking reaction;
(2) Condensing the product obtained in the step (1), and then feeding the product into a distillation separation system to obtain pure isopropanolamine and 1, 2-propane diamine;
wherein:
the temperature of the mixed gas of ammonia and water in the step (1) is 300-400 ℃;
the volume ratio of the ammonia gas to the water vapor in the step (1) is 1;
the pressure of the contact cracking reaction in the step (1) is 15-20 atmospheric pressures, and the reaction time is 40-70min.
2. The process for the production of isopropanolamine and 1, 2-propanediamine from the cleavage of 2, 5-dimethylpiperazine according to claim 1, characterized in that: the Co-Ni-Pd/Al 2 O 3 The catalyst comprises, by weight of metal oxide, coO accounting for 1-3% of the weight of the catalyst, niO accounting for 1-3% of the weight of the catalyst, and PdO accounting for 1-4% of the weight of the catalyst.
3. The method for producing isopropanolamine and 1, 2-propanediamine from the cracking of 2, 5-dimethylpiperazine according to claim 1, characterized in that: the Co-Ni-Pd/Al 2 O 3 The pore volume of (A) is 0.4-0.6ml/g, the specific surface area is 250-350m 2 /g。
4. The method for producing isopropanolamine and 1, 2-propanediamine from the cracking of 2, 5-dimethylpiperazine according to claim 1, characterized in that: the Co-Ni-Pd/Al 2 O 3 The preparation method of the catalyst comprises the following steps:
(1) Adding a sodium hydroxide solution into aluminum hydroxide, uniformly mixing, adding nitric acid for neutralization, then aging, filtering, washing, rolling ball molding, drying and roasting to prepare a spherical alumina carrier with the diameter of 3-5 mm;
(2) Mixing nitrate solutions of Co, ni and Pd according to a specific ratio to prepare a catalyst impregnation liquid, pre-impregnating an alumina carrier to obtain a wet-ball carrier, drying and roasting;
(3) Cooling the catalyst precursor prepared in the step (2), soaking the catalyst precursor in the catalyst soaking solution prepared in the step (2), taking out the catalyst precursor, drying and roasting the catalyst precursor to obtain Co-Ni-Pd/Al 2 O 3 A catalyst.
5. The process for the production of isopropanolamine and 1, 2-propanediamine from the cleavage of 2, 5-dimethylpiperazine according to claim 4, characterized in that:
adding a sodium hydroxide solution in the step (1), mixing for 2-4h, adding nitric acid, and neutralizing for 20-50min;
in the step (1), the aging temperature is 60-90 ℃, and the aging time is 4-6h; then washing with water;
in the step (1), the drying temperature is 90-130 ℃, and the drying time is 4-6h; the roasting temperature is 250-450 ℃, and the roasting time is 2-3h.
6. The process for the production of isopropanolamine and 1, 2-propanediamine from the cleavage of 2, 5-dimethylpiperazine according to claim 4, characterized in that: in the step (2), the mass fraction of the cobalt nitrate solution is 10-30%; the mass fraction of the molybdenum nitrate solution is 10-30%; the mass fraction of the palladium nitrate solution is 10-30%; the pre-impregnation time in the step (2) is 2-3h.
7. The process for the production of isopropanolamine and 1, 2-propanediamine from the cleavage of 2, 5-dimethylpiperazine according to claim 4, characterized in that: cooling to 30-50 ℃ in the step (3), and soaking for 2-3h; and (3) adopting equal-volume impregnation when impregnating in the impregnation liquid in the step (2) and the step (3).
8. The process for the production of isopropanolamine and 1, 2-propanediamine from the cleavage of 2, 5-dimethylpiperazine according to claim 4, characterized in that: the drying and roasting process parameters in the step (2) and the step (3) are the same, the drying temperature is 90-130 ℃, and the drying time is 2-6h; the roasting temperature is 250-450 ℃, and the roasting time is 2-3h.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB810916A (en) * | 1955-01-11 | 1959-03-25 | Dow Chemical Co | Utilization of by-products from manufacture of 2,5-dimethyl-piperazine |
| CN102718661A (en) * | 2012-06-26 | 2012-10-10 | 西安近代化学研究所 | Coproduction method of 1, 2-propanediamine and dimethyl piperazine |
| CN108503608A (en) * | 2018-03-26 | 2018-09-07 | 吴彦彬 | A kind of preparation method of 1,4- lupetazins |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB810916A (en) * | 1955-01-11 | 1959-03-25 | Dow Chemical Co | Utilization of by-products from manufacture of 2,5-dimethyl-piperazine |
| CN102718661A (en) * | 2012-06-26 | 2012-10-10 | 西安近代化学研究所 | Coproduction method of 1, 2-propanediamine and dimethyl piperazine |
| CN108503608A (en) * | 2018-03-26 | 2018-09-07 | 吴彦彬 | A kind of preparation method of 1,4- lupetazins |
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