CN1429660A - Skeletal nickel catalyst and its manufacturing method and use - Google Patents
Skeletal nickel catalyst and its manufacturing method and use Download PDFInfo
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- CN1429660A CN1429660A CN 01145278 CN01145278A CN1429660A CN 1429660 A CN1429660 A CN 1429660A CN 01145278 CN01145278 CN 01145278 CN 01145278 A CN01145278 A CN 01145278A CN 1429660 A CN1429660 A CN 1429660A
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- Prior art keywords
- doped element
- nickel catalyst
- aluminium
- skeletal nickel
- weight ratio
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims description 56
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 27
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 21
- 239000000956 alloy Substances 0.000 claims abstract description 21
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 150000004985 diamines Chemical class 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 239000004411 aluminium Substances 0.000 claims description 26
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 26
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 6
- 230000000737 periodic effect Effects 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910001325 element alloy Inorganic materials 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 4
- 238000003723 Smelting Methods 0.000 abstract description 3
- 230000029087 digestion Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 230000009466 transformation Effects 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 229910000990 Ni alloy Inorganic materials 0.000 description 3
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 241001253206 Andrias Species 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 240000003936 Plumbago auriculata Species 0.000 description 1
- 241001417490 Sillaginidae Species 0.000 description 1
- 241001062472 Stokellia anisodon Species 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000001118 alkylidene group Chemical group 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 125000004966 cyanoalkyl group Chemical group 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- Catalysts (AREA)
Abstract
A skeletal Ni-catalyst is prepared from Ni, Al and doping elements as raw materials containing at least one chosen from family IV, VI, or VIII through smelting alloy, cooling, breaking and digestion. It can be used for hydroreducing the long-chain dinitrile to become diamine with high transform rate.
Description
Technical field
The present invention relates to catalyst field, relate in particular to a kind of skeleton type catalyst and manufacture method thereof and purposes.
Background technology
Skeleton nickel is the catalyzer that extensively is applied to carrying out in industry and the laboratory hydrogenation, its general manufacture method is for to digest (chemical erosion) with basic solution to the nickelalloy that contains aluminium, and the catalyzer that makes has the nickel crystal accumulation body of high-specific surface area and variable remaining aluminium.
People expect that catalyzer has high activity, selectivity and stability, and this three property is inseparable with other performance, have done a lot of work for these three property people that improve catalyzer for a long time.In skeleton nickel, add promotor such as titanium, chromium, iron, cobalt, tantalum, zirconium and can improve the electronic structure of skeleton nickel, thereby improve its performance, its mechanism is: the best catalytic activation lattice parameter of hydrogen is 3.0～4.08 , and above-mentioned promotor has corresponding crystallization geometric condition and electronic structure, its crystallization generally is the center of area or body centred cubic crystal, and lattice parameter is 2.4～4.08 .
Doped F e element can make above-mentioned lattice parameter mate more in nickelalloy, by common alloy doping techniques, smelts when being molten state at nickel/aluminium alloy, and one or many joins wherein.But when mixing, multiple element in the alloy is not to reach uniform state, so this may make interior generation of catalyzer obviously form the inhomogeneous of variation or hotchpotch content, this phenomenon ascribes to metallurgical out of control, and may form the deleterious coordination structure of catalyzer, influence catalyst activity, selectivity and stability, thereby influence its catalytic efficiency.
Summary of the invention
Purpose of the present invention is exactly to provide the higher skeletal nickel catalyst of a kind of catalytic efficiency and manufacture method and purposes for the defective that overcomes above-mentioned prior art existence.
Purpose of the present invention can be achieved through the following technical solutions: a kind of skeletal nickel catalyst, this catalyzer is a raw material with nickel, aluminium, doped element, it is characterized in that, doped element has a kind of IV in the periodic table of elements, VI, VIII family of being selected from least in the described raw material, and the weight ratio of this doped element and aluminium is 5～80%.
Described doped element is Fe.
Described doped element is Fe, Cr, Ti.
The weight ratio of described doped element and aluminium is 10～50%.
The weight ratio of described doped element and aluminium is 10～20%.
The weight ratio of described doped element and aluminium is 20～30%.
The weight ratio of described doped element and aluminium is 30～40%.
The weight ratio of described doped element and aluminium is 40～50%.
The manufacture method of aforesaid skeletal nickel catalyst is characterized in that, this method comprises following processing step:
1) takes by weighing required nickel, aluminium, doped element alloy compositions respectively, wherein have a kind of IV, VI, VIII family that is selected from the periodic table of elements in the doped element at least, the weight ratio of doped element and aluminium is 5～80%, these metals are put in heating unit, be heated to fusing, and suitable in addition stirring, make it to mix;
2) the fused alloy is poured in the mould, and pour into cold water make it the cooling;
3) will cool off good alloy block and pulverize, grind to form the above fine powder of 100 orders;
4) above-mentioned ground alloy fine powder is slowly joined in NaOH or the KOH solution, make its temperature be controlled at 50～60 ℃, after treating that alloy powder adds, heat tracing 60 minutes, temperature is controlled at 80～105 ℃, leach wherein solid then, be washed till neutrality, and preserve standby with alcohol-pickled back with distilled water.
The purposes of aforesaid skeletal nickel catalyst is characterized in that, it is the reaction of long-chain diamines that described skeletal nickel catalyst is used for long-chain dintrile hydrogenating reduction.
Described long-chain dintrile can be represented with following formula (I):
NC-R-CN????(I)
To represent the C atomicity be 10～14 straight or branched alkylidene group to R in the formula.
Embodiment
Below in conjunction with specific embodiment technical solution of the present invention is described further.Embodiment 1
One. a kind of skeletal nickel catalyst, this catalyzer are that raw material is made with nickel, aluminium, doped element, and described doped element is Fe, and the weight ratio of this doped element and aluminium is 40%.
Two. the manufacturing of above-mentioned skeletal nickel catalyst
The smelting of step 1) alloy:
Desired raw material is: metallic nickel, and purity 〉=98%,
Metallic aluminium, purity 〉=99%,
Electrolytic iron, purity 〉=99%;
Above-mentioned materials is cut into small pieces earlier, takes by weighing nickel 300 grams then respectively, aluminium 500 grams, electrolytic iron 200 grams are put into plumbago crucible to them again, place medium-frequency induction furnace to smelt 30～60 minutes, treat fusion backsight situation agitation as appropriate, pour in the punching block after melt is luminous;
Step 2) cooling of alloy:
Cold water is poured into rapidly in the punching block, obtained alloy block;
The pulverizing of step 3) alloy:
The alloy block knock fritter that obtains, and then these fritters are ground to form fine powder more than 100 orders;
The digestion of step 4) alloy:
Preparing 500ml concentration under the room temperature in the 500ml beaker is the NaOH solution of 25% (weight), move in the 1000ml beaker, in the 50ml beaker, take by weighing the above-mentioned alloy fine powder of 15 grams, with little spoon will claim the alloy fine powder slowly add in the above-mentioned 1000ml beaker, keep in the beaker solution temperature about 55 ℃ with cooling bath, after treating that alloy powder adds and solution stops to seethe with excitement, be heated to 80～105 ℃, kept 60 minutes, the solid that obtains in the above-mentioned 1000ml beaker is separated out in left-falling stroke, and being washed till pH value with distilled water is 6.7～7, with the solid that obtains with alcohol-pickled 2 times, obtain the 2# skeletal nickel catalyst, move in the sample plasma bottle with cover preserve standby.
Three. above-mentioned skeletal nickel catalyst is applied to the experiment that long-chain dintrile catalytic hydrogenation becomes the long-chain diamines
Experimental installation adopts the autoclave that has magnetic stirring apparatus and steam, cold water temperature controlling system of 200ml.Experimental raw is: 12 carbon dintrile zero pour 〉=20 ℃
Alcohol concn 〉=95%, PH＜7
KOH ethanolic soln concentration=25%
Catalyzer PF-raneyNi of the present invention
Hydrogen pressure 10～15Mpa
Take by weighing 12 carbon dintrile, 20 grams respectively, ethanol 30 grams, concentration is ethanolic soln 1.5 grams of 25% KOH, the skeletal nickel catalyst 10 that makes with the inventive method restrains, put into autoclave in the lump, be evacuated earlier after the autoclave sealing, feed hydrogen then and clean secondary, the water steam-heated cal(l)andria is warmed up to 40～50 ℃ again, opens magnetic force bob agitator simultaneously.
Keeping the hydrogen pressure in the autoclave earlier is 1.0Mpa, and the time is 5 minutes, waits for when hydrogen pressure begins to descend, hydrogenation begins, and notes temperature in the still is controlled in 60～100 ℃ record hydrogenation number of times, after equipressure is stable, begin insulation, temperature remains on about 100 ℃, pressure is at 2.5Mpa, close magnetic stirring apparatus after about 20 minutes, slowly discharge pressure to 0 in the still, open autoclave, treat to tell clear liquid after the sedimentation, prepare to analyze.
Embodiment 2
Basic operational steps is with embodiment 1, and its difference is that the doped element in the skeletal nickel catalyst product is Fe, and the weight ratio of this doped element and aluminium is 80%; In addition, skeletal nickel catalyst step of manufacturing 1) in the smelting of alloy, the raw material that takes by weighing is: nickel 100 grams; Aluminium 500 grams; Electrolytic iron 400 grams, the skeleton nickel that obtains is the 3# catalyzer; Other is identical with embodiment 1.
During now a kind of novel skeleton nickel of the present invention and common skeleton nickel are reduced to the catalytic hydrogenation reaction of diamines to the long-chain dintrile catalytic efficiency experimental data is listed in the table below:
Table one embodiment interpretation of result and correlation data
| The 1# catalyzer | Transformation efficiency (%) | The 2# catalyzer | Transformation efficiency (%) | The 3# catalyzer | Transformation efficiency (%) |
| ????1-1 | ????87.63 | ????2-2 | ????94.17 | ????3-2 | ????93.43 |
| ????1-2 | ????81.8 | ????2-3 | ????93.38 | ????3 *-1 | ????94.74 |
| ????1 *-1 | ????90.32 | ????2 *-1 | ????93.42 | ????3 *-2 | ????96.53 |
| ????1 *-2 | ????91.66 | ????2 *-2 | ????91.63 | ????3 *-3 | ????94.94 |
| ????2 *-3 | ????93.54 |
Remarks: 2#, 3# catalyzer are the PF-Raney Ni that makes with the inventive method.The 1# catalyzer is common commercially available Raney Ni.The expression of band " * " is used for the second time.
Now collecting the present invention is applied to a long-chain production of resins factory dintrile catalytic hydrogenation and becomes diamines transformation efficiency field data (is purpose with the test) for your guidance:
| Adopt common Raney Ni | ??89.5 | ??84.3 | ??92.9 | ??89.4 | ??90.9 | ??94.3 |
| Adopt PF-Raney Ni of the present invention | ??91.5 | ??94.4 | ??94.5 | ??96.8 | ??95.0 | ??92.1 |
From above testing data as can be seen, formula for a product advanced person of the present invention, technology is reasonable, and it is applied to long-chain dintrile hydrogenating reduction is the reaction of diamines, can improve transformation efficiency greatly.
Claims (10)
1. skeletal nickel catalyst, this catalyzer is a raw material with nickel, aluminium, doped element, it is characterized in that, and doped element has a kind of IV in the periodic table of elements, VI, VIII family of being selected from least in the described raw material, and the weight ratio of this doped element and aluminium is 5～80%.
2. skeletal nickel catalyst according to claim 1 is characterized in that, described doped element is Fe.
3. skeletal nickel catalyst according to claim 1 is characterized in that, described doped element is Fe, Cr, Ti.
4. skeletal nickel catalyst according to claim 1 is characterized in that, the weight ratio of described doped element and aluminium is 10～50%.
5. skeletal nickel catalyst according to claim 3 is characterized in that, the weight ratio of described doped element and aluminium is 10～20%.
6. skeletal nickel catalyst according to claim 3 is characterized in that, the weight ratio of described doped element and aluminium is 20～30%.
7. skeletal nickel catalyst according to claim 3 is characterized in that, the weight ratio of described doped element and aluminium is 30～40%.
8. skeletal nickel catalyst according to claim 3 is characterized in that, the weight ratio of described doped element and aluminium is 40～50%.
9. the manufacture method of skeletal nickel catalyst as claimed in claim 1 is characterized in that, this method comprises following processing step:
1) takes by weighing required nickel, aluminium, doped element alloy compositions respectively, wherein have a kind of IV, VI, VIII family that is selected from the periodic table of elements in the doped element at least, the weight ratio of doped element and aluminium is 5～80%, these metals are put in heating unit, be heated to fusing, and suitable in addition stirring, make it to mix;
2) the fused alloy is poured in the mould, and pour into cold water make it the cooling;
3) will cool off good alloy block and pulverize, grind to form the above fine powder of 100 orders;
4) above-mentioned ground alloy fine powder is slowly joined in NaOH or the KOH solution, make its temperature be controlled at 50～60 ℃, after treating that alloy powder adds, heat tracing 60 minutes, temperature is controlled at 80～105 ℃, leach wherein solid then, be washed till neutrality, and preserve standby with alcohol-pickled back with distilled water.
10. the purposes of skeletal nickel catalyst as claimed in claim 1 is characterized in that, it is the reaction of long-chain diamines that described skeletal nickel catalyst is used for long-chain dintrile hydrogenating reduction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01145278 CN1429660A (en) | 2001-12-31 | 2001-12-31 | Skeletal nickel catalyst and its manufacturing method and use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01145278 CN1429660A (en) | 2001-12-31 | 2001-12-31 | Skeletal nickel catalyst and its manufacturing method and use |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1429660A true CN1429660A (en) | 2003-07-16 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 01145278 Pending CN1429660A (en) | 2001-12-31 | 2001-12-31 | Skeletal nickel catalyst and its manufacturing method and use |
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| Country | Link |
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| CN (1) | CN1429660A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100366527C (en) * | 2004-03-02 | 2008-02-06 | 复旦大学 | Efficient Quenching Skeleton Nickel Catalyst for Hydrogenation of 2-Ethylanthraquinone to Hydrogen Peroxide |
| CN102407152A (en) * | 2011-09-30 | 2012-04-11 | 上海师范大学 | Skeleton nickel-phosphorus catalyst and preparation method and application thereof |
| RU2650896C1 (en) * | 2017-07-05 | 2018-04-18 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Ивановский государственный химико-технологический университет" (ИГХТУ) | Method for removing residual aluminium from nickel skeleton catalyst |
| CN110841647A (en) * | 2019-12-04 | 2020-02-28 | 大连理工大学 | A kind of method for recycling waste framework nickel catalyst |
-
2001
- 2001-12-31 CN CN 01145278 patent/CN1429660A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100366527C (en) * | 2004-03-02 | 2008-02-06 | 复旦大学 | Efficient Quenching Skeleton Nickel Catalyst for Hydrogenation of 2-Ethylanthraquinone to Hydrogen Peroxide |
| CN102407152A (en) * | 2011-09-30 | 2012-04-11 | 上海师范大学 | Skeleton nickel-phosphorus catalyst and preparation method and application thereof |
| RU2650896C1 (en) * | 2017-07-05 | 2018-04-18 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Ивановский государственный химико-технологический университет" (ИГХТУ) | Method for removing residual aluminium from nickel skeleton catalyst |
| CN110841647A (en) * | 2019-12-04 | 2020-02-28 | 大连理工大学 | A kind of method for recycling waste framework nickel catalyst |
| CN110841647B (en) * | 2019-12-04 | 2021-05-14 | 大连理工大学 | Method for recycling waste skeleton nickel catalyst |
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