CN101829581B - Catalyst for amination of ethanolamine to sysnthsize ethylene diamine and preparation method thereof - Google Patents
Catalyst for amination of ethanolamine to sysnthsize ethylene diamine and preparation method thereof Download PDFInfo
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- CN101829581B CN101829581B CN 201010168669 CN201010168669A CN101829581B CN 101829581 B CN101829581 B CN 101829581B CN 201010168669 CN201010168669 CN 201010168669 CN 201010168669 A CN201010168669 A CN 201010168669A CN 101829581 B CN101829581 B CN 101829581B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 75
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 title claims abstract description 38
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000005576 amination reaction Methods 0.000 title claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 24
- 239000002184 metal Substances 0.000 claims abstract description 24
- 239000011148 porous material Substances 0.000 claims abstract description 22
- 238000007598 dipping method Methods 0.000 claims abstract description 14
- 229910052802 copper Inorganic materials 0.000 claims abstract description 13
- 229910052702 rhenium Inorganic materials 0.000 claims abstract description 10
- 239000012266 salt solution Substances 0.000 claims abstract description 9
- 229910052742 iron Inorganic materials 0.000 claims abstract description 7
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 7
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 6
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 6
- 229910017709 Ni Co Inorganic materials 0.000 claims abstract description 3
- 229910003267 Ni-Co Inorganic materials 0.000 claims abstract description 3
- 229910003262 Ni‐Co Inorganic materials 0.000 claims abstract description 3
- 230000004913 activation Effects 0.000 claims description 18
- 238000001291 vacuum drying Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 9
- 230000008030 elimination Effects 0.000 claims description 8
- 238000003379 elimination reaction Methods 0.000 claims description 8
- 229910021645 metal ion Inorganic materials 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 7
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 5
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 238000006424 Flood reaction Methods 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 34
- 230000001588 bifunctional effect Effects 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 13
- 230000000694 effects Effects 0.000 description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 230000009514 concussion Effects 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 229940031098 ethanolamine Drugs 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910000497 Amalgam Inorganic materials 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- UPCWOUOJDQAHJL-UHFFFAOYSA-N N.ClCC(=O)Cl Chemical compound N.ClCC(=O)Cl UPCWOUOJDQAHJL-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000008361 aminoacetonitriles Chemical class 0.000 description 1
- 230000002528 anti-freeze Effects 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002171 ethylene diamines Chemical class 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- OZFKPPQRIOJHTD-UHFFFAOYSA-N formaldehyde;formonitrile Chemical compound O=C.N#C OZFKPPQRIOJHTD-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000003516 soil conditioner Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
Abstract
The invention discloses a catalyst for amination of ethanolamine to sysnthsize ethylene diamine and a preparation method thereof. The catalyst is prepared by using a Ni-Co bifunctional reactive component as a base stock and adding mixing metal of two or more of Cu, Fe, Zn, Cr and Re to be loaded on a porous material carrier, wherein in the catalyst, the content of the porous material carrier accounts for 65-90 percent by weight, and the content of the mixing metal accounts for 10-35 percent by weight. The preparation method of the catalyst comprises the steps of: dipping the porous material in a metal salt solution of Ni, Co, Cu and the like twice, and then roasting at high temperature. The service life of the catalyst lasts for 400 hours, the conversion rate of the ethanolamine reaches 68.85 percent and the selectivity of the ethylene diamine reaches 71.05 percent.
Description
Technical field
The invention belongs to the chemical catalyst preparing technical field, specifically is a kind of Catalysts and its preparation method that is used for amination of ethanolamine to sysnthsize ethylene diamine.
Background technology
Ethylenediamine (ethylenediamine; EDA) have another name called 1; 2-diaminoethanes, ethylene diamine are important chemical material and fine-chemical intermediate, have alkalescence and surface-active characteristics; Be widely used in can be used for producing chelating agent, insect-proof agent, soil conditioner, lubricant, rubber accelerator, emulsifying agent, antifreeze and organic solvent etc. in the industries such as organic compound, macromolecular compound, medicine, dyestuff, agricultural chemicals.
The production method of ethylenediamine is a lot, and dichloroethane law, Girbotal process, ethene ammoniation process, formaldehyde-hydrogen cyanide method, diethylene glycol (DEG) ammoniation process, chloracetyl chloride ammonia process and aminoacetonitriles hydrogenation method are arranged.But it mainly is dichloroethane law and Girbotal process that the method for producing ethylenediamine is gone up in industry at present.
Ethylenediamine is produced in the amination in the presence of catalyst of monoethanolamine and ammonia; Because intermediate amine has higher reactivity than ammonia; Therefore reaction inevitably produces complicated polyalkylenepolyamines accessory substance, makes the yield of ethylenediamine reduce and causes the product separation difficulty.Method commonly used can improve product selectivity, but conversion ratio reduces, and has influenced the production capacity of ethylenediamine.Therefore, need a kind of catalyst to have the ability that not only product is had high selectivity, and keep good amination conversion ratio, under the better situation, catalyst is only selective by the substituted product of amido to active function groups.
The research of amination catalysis is had it long ago, and correlation technique also is known in the art, in Preparation of Catalyst of the present invention, quotes and reference.US4209424 has reported the influence of nickel loading to catalyst activity, finds the increase along with nickel loading, and the conversion ratio of feed ethanol amine improves constantly, but reaction pair cyclammonium (like piperazine) has higher selectivity.US4123462 points out that catalyst activity and carrier material have confidential relation, changes the surface propertys such as surface area, hole dimension, pore volume and support shapes of carrier, will influence activity of such catalysts within the specific limits.
U.S. Pat 5068330 adopts different nickel based metal catalyst, adds noble metals such as Ir, Pt, Ru, and in the time of 120～300 ℃, monoethanolamine conversion ratio 20%～45% generates ethylenediamine selectivity 15%～55%, diethylenetriamine 10%～20%.This catalyst monoethanolamine conversion ratio and the equal difficulty of ethylenediamine selectivity reach requirement, and in preparation process, add noble metal repeatedly continuously, have increased the complexity and the production cost of technological operation.
US6534441 has reported a kind of Ni-Re-B/Al
2O
3Catalyst, this catalyst can make the ethylenediamine selectivity be increased to 70%～80%, but the loss meeting pollution products of B in the reaction causes difficulty to separation, and interpolation B makes the Preparation of catalysts process comparatively complicated.But certainly, when adding components such as La, Ca, Mg, Sr, Li, K, Ba, Ce, W, Fe, Cu, Zn, Ti, B, Mn in the preparation, improved the stability of catalyst, improved life-span and mechanical strength.
Summary of the invention
The objective of the invention is provides a kind of catalyst of amination of ethanolamine to sysnthsize ethylene diamine of high selectivity in order to overcome deficiency and the defective that prior art exists.
The catalyst that is used for amination of ethanolamine to sysnthsize ethylene diamine that the present invention proposes, it is to be base-material with Ni-Co dual-active property component, adds two or more hybrid metals such as Cu, Fe, Zn, Cr and Re and is carried on the porous material carrier preparation and gets.
Above-described porous material carrier is Al
2O
3, TiO
2, SiO
2And ZrO
2In any one or more than one amalgam.The specific area of porous material is 50～250m
2/ g, pore volume are 0.2～1.0ml/g.
Porous material carrier weight percentage in the said catalyst is 65～90%, and the hybrid metal weight percentage is 10～35%; The weight percentage of each metal is respectively in the hybrid metal: Ni1～20%, Co1～20%, Cu1～10%, Fe1～10%, Zn0.1～5%, Cr0.1～5% and Re0.01～1%.
Above-described amination of ethanolamine to sysnthsize ethylene diamine Preparation of catalysts method, the preparation process is made up of following each step:
(1) porous material carrier dry 1～3h in 200 ℃ vacuum drying chamber, the metal salt solution that will contain Ni, Co, Cu, Fe, Zn, Cr and Re then holds in the container of carrier slow the adding, in ultrasonic wave, floods 1～3h; Described slaine is nitrate or its chloride.
(2) the unnecessary liquid of elimination has been adsorbed with the carrier of metal ion, dry 1～3h in 100～200 ℃ vacuum drying chamber, and dry continued is flooded in remaining solution;
(3) carrier 350～650 ℃ of following roasting 2～8h in chamber type electric resistance furnace through twice dipping make catalyst.
The catalyst that is used for monoethanolamine and ammonia synthesis ethylenediamine provided by the invention, catalyst need carry out activation before using.Activation is carried out in atmosphere of hydrogen, and nitrogen and hydrogen volume were than 1: 1～1: 8.Activation temperature is heated to 250 ℃ and kept 1～3 hour from room temperature, is heated to 300 ℃～450 ℃ continued activation 2～5 hours then.
Advantage of the present invention:
(1) catalyst provided by the invention has stronger activity and excellent selectivity, and the monoethanolamine conversion ratio reaches 68.85%, and the selectivity of ethylenediamine reaches 71.05%, when producing a large amount of target product ethylenediamines, produces the accessory substance of relatively small amount;
(2) catalyst activity wider range can use under low material concentration, compares with other catalyst, can under the situation of identical or less raw material, obtain more high activity and selectivity;
(3) catalyst has excellent mechanical intensity and stability, and the life-span reaches more than the 400h, can satisfy the needs of autoclave and shell and tube reactor commercial production ethylenediamine.
The specific embodiment
In order to understand the present invention better, further set forth below in conjunction with embodiment, but these embodiment should not be construed as any restriction of the present invention.
Embodiment 1
1.1 Preparation of Catalyst
(1) with 30.63gNi (NO
3)
2, 12.45gCo (NO
3)
2, 8.51gCu (NO
3)
2, 11.53gCr (NO
3)
3And 0.35g (NH
4)
3ReO
5Be dissolved in wiring solution-forming in the deionized water respectively;
(2) take by weighing 102.02g microspheric form Al
2O
3Carrier, Al
2O
3Specific area be 180m
2/ g, pore volume are 0.6ml/g, and dry 2h in 200 ℃ vacuum drying chamber mixes dried carrier and step (1) gained metal salt solution then and adds in the beaker and concussion dipping 2h in ultrasonic wave;
(3) the unnecessary liquid of elimination has been adsorbed with the carrier of metal ion, and dry 3h in 150 ℃ vacuum drying chamber continues in remaining solution, to flood then;
(4) carrier 550～650 ℃ of following roasting 3h in chamber type electric resistance furnace through twice dipping make catalyst.
1.2, catalyst activation
Catalyst is reduction activation in tubular reactor, through about 2h temperature is heated to 250 ℃ and kept 1 hour, makes H simultaneously
2And N
2Air communication with 200mL/min:40mL/min is crossed reaction tube, continues to be heated to 350 ℃ and constant temperature activation 3 hours.Stop heating, the maintenance ventilation is flowed till reaction tube is cooled to room temperature, transfers to the catalyst of activation carefully then to be full of N
2The bottle in store for future use.
1.3, catalyst activity test: adopt autoclave and tubular reactor to distinguish synthesis of ethylenediamine
Autoclave is synthetic: catalyst and MEA drop in the autoclave, ammonia-alcohol ratio 5: 1, catalyst concentration 1.5%, reaction pressure 12MPa, reaction time 4h, 180 ℃ of reaction temperatures.
Shell-and-tube reactor is synthetic: behind the catalyst activation, with MEA, ammonia and hydrogen according to mol ratio charging in 1: 5: 0.1, MEA liquid air speed 0.3h
-1, reaction pressure 8MPa, 200 ℃ of reaction temperatures, circulation successive reaction 100h.
The gained result is:
The catalyst weight percentage composition
Al
2O
3Carrier: 85%; Hybrid metal: 15%;
Wherein: Ni
2+: 8.2%, Co
2+: 2.1%, Cu
2+: 2.4%, Cr
3+: 2.1%, Re
7+: 0.2%.
Autoclave is synthetic: the conversion ratio of MEA is 69.71%, and the selectivity of ethylenediamine is 67.65%.
Shell-and-tube reactor is synthetic: the conversion ratio of MEA is 68.85%, and the selectivity of ethylenediamine is 71.05%.
Embodiment 2:
2.1, Preparation of Catalyst
(1) with 35.86gNi (NO
3)
2, 28.45gCo (NO
3)
2, 7.09gCu (NO
3)
2, 1.05gZn (NO
3)
2And 0.52g (NH
4)
3ReO
5Be dissolved in wiring solution-forming in the deionized water respectively;
(2) take by weighing 99.60g TiO
2Carrier, TiO
2Specific area be 95m
2/ g, pore volume are 0.6ml/g, and dry 2h in 200 ℃ vacuum drying chamber mixes dried carrier and step (1) gained metal salt solution then and adds in the beaker and concussion dipping 1.5h in ultrasonic wave;
(3) the unnecessary liquid of elimination, what obtain is adsorbed with carriers of metal ions dry 2h in 150 ℃ vacuum drying chamber, continues then in remaining solution, to flood;
(4) carrier 500～600 ℃ of following roasting 4h in chamber type electric resistance furnace through twice dipping make catalyst.
2.2, catalyst activation and catalyst activity test course of reaction is with embodiment 1.
The gained result is:
The catalyst weight percentage composition
TiO
2Carrier: 83%; Hybrid metal: 17%;
Wherein: Ni
2+: 9.6%, Co
2+: 4.8%, Cu
2+: 2.0%, Zn
2+: 0.3%, Re
7+: 0.3%.
Autoclave is synthetic: the conversion ratio of MEA is 83.34%, and the selectivity of ethylenediamine is 48.25%.
Shell-and-tube reactor is synthetic: the conversion ratio of MEA is 78.34%, and the selectivity of ethylenediamine is 54.45%.
Embodiment 3:
3.1 Preparation of Catalyst
(1) with 33.24gNi (NO
3)
2, 52.75gCo (NO
3)
2, 13.82gCu (NO
3)
2And 0.52g (NH
4)
3ReO
5Be dissolved in wiring solution-forming in the deionized water respectively;
(2) take by weighing 93.60g SiO
2-Al
2O
3Carrier, SiO
2-Al
2O
3Specific area be 150m
2/ g, pore volume are 0.5ml/g, and dry 2h in 200 ℃ vacuum drying chamber mixes dried carrier and step (1) gained metal salt solution then and adds in the beaker and concussion dipping 3h in ultrasonic wave;
(3) the unnecessary liquid of elimination has been adsorbed with carrier dry 2.5h in 150 ℃ vacuum drying chamber of metal ion, continues then in remaining solution, to flood;
(4) carrier 450～550 ℃ of following roasting 6h in chamber type electric resistance furnace through twice dipping make catalyst.
3.2, catalyst activation and catalyst activity test course of reaction is with embodiment 1.
The gained result is:
The catalyst weight percentage composition
SiO
2-Al
2O
3Carrier: 78%, hybrid metal: 22%;
Wherein: Ni
2+: 8.9%, Co
2+: 8.9%, Cu
2+: 3.9%, Re
7+: 0.3%%.
Autoclave is synthetic: the conversion ratio of MEA is 66.11%, and the selectivity of ethylenediamine is 67.95%.
Shell-and-tube reactor is synthetic: the conversion ratio of MEA is 62.27%, and the selectivity of ethylenediamine is 69.23%.
Embodiment 4:
4.1 Preparation of Catalyst
(1) with 35.86gNi (NO
3)
2, 44.45gCo (NO
3)
2, 3.57gCuCl
2, 4.88gFeCl
3And 0.17g (NH
4)
3ReO
5Be dissolved in wiring solution-forming in the deionized water respectively;
(2) take by weighing 96.10g SiO
2Carrier, SiO
2Specific area be 250m
2/ g, pore volume are 0.4ml/g, and dry 2h in 200 ℃ vacuum drying chamber mixes dried carrier and step (1) gained metal salt solution then and adds in the beaker and concussion dipping 1.5h in ultrasonic wave;
(3) the unnecessary liquid of elimination, what obtain is adsorbed with carriers of metal ions dry 1.5h in 150 ℃ vacuum drying chamber, continues then in remaining solution, to flood;
(4) carrier 400～500 ℃ of following roasting 7h in chamber type electric resistance furnace through twice dipping make catalyst.
4.2, catalyst activation and catalyst activity test course of reaction is with embodiment 1.
The gained result is:
The catalyst weight percentage composition
SiO
2Carrier: 80%, hybrid metal: 20%;
Wherein: Ni
2+: 9.6%, Co
2+: 7.5%, Cu
2+: 1.4%, Fe
3+: 1.4%:Re
7+: 0.1%.
Autoclave is synthetic: the conversion ratio of MEA is 50.13%, and the selectivity of ethylenediamine is 62.02%.
Shell-and-tube reactor is synthetic: the conversion ratio of MEA is 46.37%, and the selectivity of ethylenediamine is 77.21%.
Embodiment 5:
5.1 Preparation of Catalyst
(1) with 16.81gNi (NO
3)
2, 22.52gCo (NO
3)
2, 5.67gCu (NO
3)
2And 0.17g (NH
4)
3ReO
5Be dissolved in wiring solution-forming in the deionized water respectively;
(2) take by weighing 107.62g TiO
2-SiO
2-Al
2O
3Carrier, TiO
2-SiO
2-Al
2O
3Specific area be 160m
2/ g, pore volume are 0.5ml/g, following dry 2h in 200 ℃ vacuum drying chamber, then with dried carrier and step (1) gained metal salt solution mix add in the beaker and in ultrasonic wave concussion flood 2.5h;
(3) the unnecessary liquid of elimination has been adsorbed with carrier dry 2.5h in 150 ℃ vacuum drying chamber of metal ion, continues then in remaining solution, to flood;
(4) carrier 350～450 ℃ of following roasting 8h in chamber type electric resistance furnace through twice dipping make catalyst.
5.2, catalyst activation and catalyst activity test course of reaction is with embodiment 1.
The gained result is:
The catalyst weight percentage composition
TiO
2-SiO
2-Al
2O
3Carrier: 90%; Hybrid metal: 10%;
Wherein: Ni
2+: 4.5%, Co
2+: 3.8%, Cu
2+: 1.6%, Re
7+: 0.1%.
Autoclave is synthetic: the conversion ratio of MEA is 58.74%, and the selectivity of ethylenediamine is 65.81%.
Shell-and-tube reactor is synthetic: the conversion ratio of MEA is 52.12%, and the selectivity of ethylenediamine is 68.22%.
Embodiment 6:
6.1 Preparation of Catalyst
(1) with 44.08gNi (NO
3)
2, 50.38gCo (NO
3)
2, 16.31gCu (NO
3)
2And 0.17g (NH
4)
3ReO
5Be dissolved in wiring solution-forming in the deionized water respectively;
(2) take by weighing 89.94g TiO
2-Al
2O
3Carrier, TiO
2-Al
2O
3Specific area be 120m
2/ g, pore volume are 0.6ml/g, and dry 2h in 200 ℃ vacuum drying chamber mixes dried carrier and step (1) gained metal salt solution then and adds in the beaker and concussion dipping 2h in ultrasonic wave;
(3) the unnecessary liquid of elimination has been adsorbed with carrier dry 1h in 150 ℃ vacuum drying chamber of metal ion, continues then in remaining solution, to flood;
(4) carrier 450～500 ℃ of following roasting 6h in chamber type electric resistance furnace through twice dipping make catalyst.
6.2, catalyst activation and catalyst activity test course of reaction is with embodiment 1.
The gained result is:
The catalyst weight percentage composition
TiO
2-Al
2O
3Carrier: 75%; Hybrid metal: 25%;
Wherein: Ni
2+: 11.8%, Co
2+: 8.5%, Cu
2+: 4.6%, Re
7+: 0.1%.
Autoclave is synthetic: the conversion ratio of MEA is 53.03%, and the selectivity of ethylenediamine is 63.42%.
Shell-and-tube reactor is synthetic: the conversion ratio of MEA is 49.71%, and the selectivity of ethylenediamine is 70.41%.
Claims (3)
1. catalyst that is used for amination of ethanolamine to sysnthsize ethylene diamine is characterized in that: this catalyst is to be base-material with Ni-Co dual-active property component, adds Cu, Fe, Zn, Cr and Re and is carried on the porous material carrier and prepares; The porous material carrier weight percentage is 65～90% in the described catalyst, and the hybrid metal weight percentage is 10～35%;
Described porous material carrier is Al
2O
3, TiO
2, SiO
2And ZrO
2In any one or more than one mixture; The specific area of porous material is 50～250m
2/ g, pore volume are 0.2～1.0ml/g;
The weight percentage of described hybrid metal is respectively: Ni1～20%; Co1～20%; Cu1～10%; Fe1～10%; Zn0.1～5%; Cr0.1～5%; Re0.01～1%.
2. the Preparation of catalysts method that is used for amination of ethanolamine to sysnthsize ethylene diamine as claimed in claim 1 is characterized in that: technical process is made up of following each step:
(1) porous material carrier dry 1～3h in 200 ℃ vacuum drying chamber, the metal salt solution that will contain Ni, Co, Cu, Fe, Zn, Cr and Re then holds in the container of carrier slow the adding, in ultrasonic wave, floods 1～3h; Described slaine is nitrate or its chloride;
(2) the unnecessary liquid of elimination has been adsorbed with the carrier of metal ion, dry 1～3h in 100～200 ℃ vacuum drying chamber, and dry continued is flooded in remaining solution;
(3) carrier 350～650 ℃ of following roasting 2～8h in chamber type electric resistance furnace through twice dipping make catalyst.
3. the catalyst that is used for amination of ethanolamine to sysnthsize ethylene diamine as claimed in claim 1; It is characterized in that: catalyst need carry out activation before using; Activation is carried out in atmosphere of hydrogen; Nitrogen and hydrogen volume be than 1: 1～1: 8, and activation temperature is heated to 250 ℃ and kept 1～3 hour from room temperature, is heated to 300 ℃～450 ℃ continued activation 2～5 hours then.
Priority Applications (1)
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| CN101982238B (en) * | 2010-10-11 | 2012-11-21 | 广西壮族自治区化工研究院 | Method for preparing ethanediamine solid catalyst by synthesis of monoethanolamine |
| CN102658162B (en) * | 2012-04-13 | 2013-10-30 | 中国科学院大连化学物理研究所 | Catalyst for synthesizing ethylene amine and method for preparing ethylene amine |
| CN107913694A (en) * | 2017-10-31 | 2018-04-17 | 山东玉皇化工有限公司 | A kind of modulating method of amination catalysis carrier and its application |
| CN107899587B (en) * | 2017-11-22 | 2021-02-05 | 山东玉皇化工有限公司 | Catalyst for amine production by fatty alcohol amination and preparation method thereof |
| CN107983367B (en) * | 2017-12-08 | 2020-10-27 | 西安近代化学研究所 | Reductive amination catalyst and preparation method thereof |
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Application publication date: 20100915 Assignee: GUANGXI LONGAN RUIFENG INDUSTRIAL & TRADING CO.,LTD. Assignor: GUANGXI RESEARCH INSTITUTE OF CHEMICAL INDUSTRY Co.,Ltd. Contract record no.: X2023980045481 Denomination of invention: Catalyst and preparation method for the synthesis of ethylenediamine from ethanolamine amine Granted publication date: 20120502 License type: Common License Record date: 20231101 |