CN1184181C - Method for preparing 1,3-propylene glycol by 3-hydroxypropionaldehyde hydrogenation - Google Patents
Method for preparing 1,3-propylene glycol by 3-hydroxypropionaldehyde hydrogenation Download PDFInfo
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- CN1184181C CN1184181C CNB011392428A CN01139242A CN1184181C CN 1184181 C CN1184181 C CN 1184181C CN B011392428 A CNB011392428 A CN B011392428A CN 01139242 A CN01139242 A CN 01139242A CN 1184181 C CN1184181 C CN 1184181C
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- hydrogenation
- ammediol
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- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 33
- AKXKFZDCRYJKTF-UHFFFAOYSA-N 3-Hydroxypropionaldehyde Chemical compound OCCC=O AKXKFZDCRYJKTF-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 238000000034 method Methods 0.000 title claims abstract description 10
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 title abstract 4
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 230000000694 effects Effects 0.000 claims abstract description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 239000002808 molecular sieve Substances 0.000 claims abstract description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 claims description 18
- 238000002360 preparation method Methods 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000000470 constituent Substances 0.000 abstract description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 4
- 239000005864 Sulphur Substances 0.000 abstract description 4
- 229910052785 arsenic Inorganic materials 0.000 abstract description 4
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 4
- 239000011574 phosphorus Substances 0.000 abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 3
- 231100000614 poison Toxicity 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052742 iron Inorganic materials 0.000 abstract description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 abstract 2
- 229940035437 1,3-propanediol Drugs 0.000 abstract 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 abstract 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 239000012295 chemical reaction liquid Substances 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 239000003440 toxic substance Substances 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 11
- 229940010552 ammonium molybdate Drugs 0.000 description 11
- 235000018660 ammonium molybdate Nutrition 0.000 description 11
- 239000011609 ammonium molybdate Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 9
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- NBBJYMSMWIIQGU-UHFFFAOYSA-N propionic aldehyde Natural products CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 5
- -1 ammediol ester Chemical class 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000007868 Raney catalyst Substances 0.000 description 2
- 229910000564 Raney nickel Inorganic materials 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 230000007096 poisonous effect Effects 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a method for preparing 1, 3-propanediol from 3-hydroxypropionaldehyde hydrogenation. The concentration of a 3-hydroxypropionaldehyde water solution as raw material expressed in percentage by weight is from 10 to 25%. Under the existence of a catalyst, two-stage hydrogenation is used for preparing the 1, 3-propanediol. the temperature of the first-stage hydrogenation is from 25 to 60 DEG C and the temperature of the second-stage hydrogenation is from 110 to 130 DEG C. the hydrogen pressure of the two-stage hydrogenation is from 4.0 to 7.0MPa and air speed is from 0.1 to 5 hr<-1>. An active constituent of the catalyst is Ni-A, wherein the A is any one of Cr, Zn, Mo or Fe, and a weight ratio of the Ni to the A is from 1:0.01 to 1:0.1. A carrier contains Al2O3 or SiO2, or simultaneously contains the molecular sieves of the both. The weight percentage content of the active constituent of the catalyst is from 30 to 60%. The catalyst used by the present invention has high activity and is not sensitive to toxic substances, such as sulphur, phosphorus, arsenic, etc., in reaction liquid, and a required hydrogenation condition is mild.
Description
Technical field
The present invention relates to be equipped with 1 by the 3-3-hydroxyl propionaldehyde hydrogenation to produce, the method for ammediol contains Ni and Cr, Zn, Mo or Fe in the catalyst activity component of employing.
Background technology
1, ammediol is a kind of broad-spectrum compound, and except that can be used for producing urethane and the ring compound, it still is a poly terephthalic acid 1, the principal monomer of ammediol ester fiber.Poly terephthalic acid 1, ammediol ester fiber are the polyester kinds of excellent performance, though just come out in the fifties, but because of 1, ammediol can't be realized industrialization, makes poly terephthalic acid 1, and the development of ammediol ester fiber stays cool for many years all the time.In recent years, along with 1, the success of ammediol suitability for industrialized production, poly terephthalic acid 1, the Application and Development of ammediol ester fiber receives publicity heavily again.At present, generate the 3-hydroxy propanal by acrolein hydration, and then make 1 by hydrogenation, ammediol is one of successful suitability for industrialized production route.By prior art as can be known, 3-3-hydroxyl propionaldehyde hydrogenation to produce 1, the preferred hydrogenation catalyst of ammediol roughly is divided into following a few class: one, Raney nickel type catalyzer, and can add the metal that some have promoting catalysis; Two, be the catalyzer of carrier with metal oxide or gac, active constituent is platinum or palladium; Three, with the molecular sieve be the catalyzer of carrier, active constituent is a nickel.Second and third class catalyzer is mainly used in the fixed-bed reactor.
As United States Patent (USP) 5,093,537 have proposed a kind of 3-of being used for 3-hydroxyl propionaldehyde hydrogenation to produce 1, and ammediol contains the Raney nickel type catalyzer of Mo, and catalyst grain size is 50m μ.Catalyst consumption is that the weight percent of catalyzer in reaction solution is 4～6%, the concentration expressed in percentage by weight of the raw material 3-hydroxy propanal aqueous solution is 10～20%, hydrogen pressure is 1.5～6.0mpa, hydrogenation temperature is 45～95 ℃, when hydrogenation time was 15～85min, the transformation efficiency of 3-hydroxy propanal reached as high as 99%.But its shortcoming is 1, and the selectivity fluctuation of ammediol is bigger, and when transformation efficiency was low, selectivity can reach 100%, but rose as transformation efficiency, and selectivity then obviously descends.In addition, because granules of catalyst is very little, the separation of catalyzer from reaction solution be difficulty quite, needs to add diatomite in advance usually in reaction solution and just can separate, and makes catalyzer to reuse like this.
At United States Patent (USP) 5,015, proposed to be used for two kinds of fixed bed hydrogenation catalyzer of 3-hydroxy propanal in 789 and 5,364,984 respectively, it consists of Ni/Al
2O
3/ SiO
2And Pt/TiO
2Ni/Al
2O
3/ SiO
2Catalyzer is because activity is lower, and particularly activity stability is relatively poor, and the reaction later stage needs continuous rising hydrogen pressure on full scale plant, the concentration of 3-hydroxy propanal can be reduced to below 0.1%.And Pt/TiO
2Catalyzer is the improvement of this catalyzer, especially aspect activity stability, improves a lot, but because platinum is easy to poisoning, so high to the sulphur in the reaction solution, phosphorus and the requirement of arsenic equal size, also can cause the increase of production cost.
Summary of the invention
Technical problem to be solved by this invention provides and a kind ofly is equipped with 1 by the 3-3-hydroxyl propionaldehyde hydrogenation to produce, the method of ammediol, the catalyzer that its adopts not only will have higher and stable catalytic activity, selectivity preferably, and insensitive to poisonous substances such as the sulphur in the reaction solution, phosphorus and arsenic, to overcome the defective that prior art exists.
Technical problem to be solved by this invention is achieved through the following technical solutions:
A kind ofly be equipped with 1 by the 3-3-hydroxyl propionaldehyde hydrogenation to produce, the method of ammediol, the concentration expressed in percentage by weight of the raw material 3-hydroxy propanal aqueous solution is 10～25%, in the presence of catalyzer, divide two-stage hydrogenation to make 1, ammediol, first section hydrogenation temperature is 25～60 ℃, second section hydrogenation temperature is 110～130 ℃, the hydrogen pressure of two-stage hydrogenation is 4.0～7.0MPa, and air speed is 0.1～5hr
-1, the activity of such catalysts component is:
Ni-A
Wherein A is any among Cr, Zn, Mo or the Fe,
The weight ratio of Ni and A is: Ni: A=1: (0.01～0.1)
Carrier is for containing Al
2O
3Or SiO
2, or containing both molecular sieve simultaneously, the weight percentage of catalyst activity component is 30～60%.
Component A is preferably Cr or Mo; The weight ratio of Ni and A is preferably Ni: A=1: (0.02～0.08).
Catalyzer can adopt the ordinary method preparation.Generally be that fine particle molecular sieve and required active metallic compound are mixed the back extruded moulding, and be cut into particle, make compound decomposition become corresponding oxide compound through high-temperature roasting again, use hydrogen reducing at last, reduce to room temperature after secluding air preserve standby.
The catalyzer that the present invention adopts is owing to added aiding catalytic component A, it can help to form highly active nickelalloy cluster active centre on the one hand, on the other hand effective modification has been carried out in the duct of catalyzer, helped the diffusion of 3-hydroxy propanal, thereby activity of such catalysts is significantly improved.It is insensitive to poisonous substances such as the sulphur in the reaction solution, phosphorus and arsenic on the other hand, and desired hydroconversion condition is also relatively gentleer, and this is very favorable to reducing the hydrogenation production cost.
Embodiment
To come below that the invention will be further described by embodiment, in an embodiment:
[embodiment 1～12]
Preparation of catalysts:
With nickelous nitrate and a kind of water-soluble cpds that contains aiding catalytic component A, be mixed with the aqueous solution according to certain ratio, add the carrier of catalyzer more in proportion, and stir.After reaching certain viscosity, extruded moulding dries in the shade again.For the intensity that improves catalyzer and make metallic compound resolve into oxide compound, more respectively 80 ℃, 300 ℃, 700 ℃ roastings 3 hours, 4 hours and 5 hours.Naturally reduce to room temperature after roasting finishes, and in the reduction reactor of packing into, when hydrogen pressure is 0.2MPa, heat up in about 4 hours of 470 ℃ of reduction, reducing degree can be judged from the water growing amount.Reduction drops to room temperature at nitrogen atmosphere after finishing, and is kept in the water standby.
The composition of each embodiment catalyzer, the starting material of component A sees Table 1.
1, the preparation of ammediol:
100 grams and 25 gram catalyzer are respectively charged into placed in-line two tubular fixed-bed reactors, first reactor charge, 100 grams, second reactor charge, 25 grams.To feed first reactor after the raw material 3-hydroxy propanal aqueous solution and the hydrogen mixing preheating, keep hydrogen pressure to carry out hydrogenation; Enter second reactor behind the first reactor outlet material heat temperature raising, keep hydrogen pressure to continue hydrogenation.Material behind the hydrogenation cools off laggard promoting the circulation of qi liquid to be separated, and liquid is analyzed wherein 3-hydroxy propanal, 1, ammediol and content of by-products with capillary chromatography.
Other concrete reaction conditions and reaction result of each embodiment sees Table 2.
Table 1.
| Component A | The starting material of component A | Ni: A (weight ratio) | Carrier | Active constituent content (%wt.) | |
| Embodiment 1 | Fe | Iron nitrate | 1∶0.04 | SiO 2-Al 2O 3 | 50.9 |
| Embodiment 2 | Zn | Zinc nitrate | 1∶0.04 | SiO 2-Al 2O 3 | 50.9 |
| Embodiment 3 | Cr | Chromium nitrate | 1∶0.04 | SiO 2-Al 2O 3 | 50.9 |
| Embodiment 4 | Mo | Ammonium molybdate | 1∶0.02 | Al 2O 3 | 50.9 |
| Embodiment 5 | Mo | Ammonium molybdate | 1∶0.04 | SiO 2 | 50.9 |
| Embodiment 6 | Mo | Ammonium molybdate | 1∶0.06 | SiO 2-Al 2O 3 | 50.9 |
| Embodiment 7 | Mo | Ammonium molybdate | 1∶0.10 | SiO 2-Al 2O 3 | 50.9 |
| Embodiment 8 | Mo | Ammonium molybdate | 1∶0.08 | SiO 2-Al 2O 3 | 50.9 |
| Embodiment 9 | Mo | Ammonium molybdate | 1∶0.04 | SiO 2-Al 2O 3 | 30.0 |
| Embodiment 10 | Mo | Ammonium molybdate | 1∶0.04 | SiO 2-Al 2O 3 | 50.0 |
| Embodiment 11 | Mo | Ammonium molybdate | 1∶0.05 | SiO 2-Al 2O 3 | 60.0 |
| Embodiment 12 | Mo | Ammonium molybdate | 1∶0.04 | SiO 2-Al 2O 3 | 40.0 |
| Embodiment 13 | Mo | Ammonium molybdate | 1∶0.04 | SiO 2-Al 2O 3 | 55.0 |
| Embodiment 14 | Mo | Ammonium molybdate | 1∶0.04 | SiO 2-Al 2O 3 | 60.0 |
Table 2.
| Material concentration (wt.%) | The one-stage hydrogenation temperature (℃) | The secondary hydrogenation temperature (℃) | Air speed (hr -1) | Hydrogen pressure (mpa) | Transformation efficiency (%) | Selectivity (%) | |
| Embodiment 1 | 12 | 50 | 110 | 3 | 6.0 | 100 | 100 |
| Embodiment 2 | 12 | 40 | 120 | 3 | 6.0 | 100 | 100 |
| Embodiment 3 | 12 | 25 | 120 | 3 | 6.0 | 100 | 100 |
| Embodiment 4 | 12 | 60 | 120 | 3 | 6.0 | 100 | 100 |
| Embodiment 5 | 12 | 50 | 120 | 3 | 7.0 | 100 | 100 |
| Embodiment 6 | 12 | 50 | 120 | 3 | 5.0 | 100 | 100 |
| Embodiment 7 | 12 | 50 | 120 | 3 | 4.0 | 100 | 100 |
| Embodiment 8 | 10 | 50 | 120 | 3 | 6.0 | 100 | 100 |
| Embodiment 9 | 18 | 50 | 120 | 3 | 6.0 | 100 | 100 |
| Embodiment 10 | 20 | 50 | 120 | 3 | 6.0 | 100 | 99 |
| Embodiment 11 | 25 | 50 | 120 | 3 | 6.0 | 100 | 99 |
| Embodiment 12 | 25 | 50 | 130 | 0.1 | 6.0 | 100 | 99 |
| Embodiment 13 | 25 | 50 | 120 | 0.5 | 6.0 | 100 | 99 |
| Embodiment 14 | 25 | 50 | 120 | 5 | 6.0 | 99 | 100 |
Claims (3)
1, a kind of by 3-hydroxy propanal continuous hydrogenation preparation 1, the method of ammediol, the concentration expressed in percentage by weight of the raw material 3-hydroxy propanal aqueous solution is 10～25%, raw material makes 1 by catalyst fixed bed minute two-stage hydrogenation, ammediol, first section hydrogenation temperature is 25～60 ℃, second section hydrogenation temperature is 110～130 ℃, the hydrogen pressure of two-stage hydrogenation is 4.0～7.0MPa, and air speed is 0.1～5hr
-1, the activity of such catalysts component is:
Ni-A
Wherein A is any among Cr, Zn, Mo or the Fe,
The weight ratio of Ni and A is: Ni: A=1: 0.01～1: 0.1,
Carrier is for containing Al
2O
3Or SiO
2, or containing both molecular sieve simultaneously, the weight percentage of catalyst activity component is 30～60%.
2, preparation 1 according to claim 1, the method for ammediol is characterized in that catalyst activity component A is Cr or Mo.
3, preparation 1 according to claim 2, the method for ammediol, the weight ratio that it is characterized in that catalyst activity component Ni and A is Ni: A=1: 0.02～1: 0.08.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011392428A CN1184181C (en) | 2001-12-27 | 2001-12-27 | Method for preparing 1,3-propylene glycol by 3-hydroxypropionaldehyde hydrogenation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011392428A CN1184181C (en) | 2001-12-27 | 2001-12-27 | Method for preparing 1,3-propylene glycol by 3-hydroxypropionaldehyde hydrogenation |
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|---|---|
| CN1428322A CN1428322A (en) | 2003-07-09 |
| CN1184181C true CN1184181C (en) | 2005-01-12 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100432194C (en) * | 2005-10-19 | 2008-11-12 | 中国石油化工股份有限公司 | A kind of paraffin hydrorefining catalyst and its preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2606314A1 (en) | 2005-04-21 | 2006-11-02 | Shell Internationale Research Maatschappij B.V. | Hydrogenation catalyst and hydrogenation method |
| CN1319920C (en) * | 2005-08-29 | 2007-06-06 | 上海华谊丙烯酸有限公司 | Method for 3- hydroxyl propionaldehyde hydrogenation to produce 1,3-propanediol |
| CN101454076A (en) | 2006-04-13 | 2009-06-10 | 国际壳牌研究有限公司 | Process for hydrogenating an aldehyde |
| US8212062B2 (en) | 2007-04-02 | 2012-07-03 | Inventure Chemical, Inc. | Production of biodiesel, cellulosic sugars, and peptides from the simultaneous esterification and alcoholysis/hydrolysis of oil-containing materials with cellulosic and peptidic content |
| US7943792B2 (en) | 2007-04-02 | 2011-05-17 | Inventure Chemical Inc. | Production of biodiesel, cellulosic sugars, and peptides from the simultaneous esterification and alcoholysis/hydrolysis of materials with oil-containing substituents including phospholipids and peptidic content |
| US7777085B2 (en) | 2008-10-01 | 2010-08-17 | Inventure Chemical, Inc. | Method for conversion of oil-containing algae to 1,3-propanediol |
| CN106588567A (en) * | 2016-11-08 | 2017-04-26 | 上海华谊能源化工有限公司 | Preparation method of 1,3-propylene glycol through hydrogenation of 3-hydroxyl propionaldehyde |
| CN107353180B (en) * | 2017-06-22 | 2020-10-23 | 江苏飞翔化工股份有限公司 | Method for preparing 1, 3-propylene glycol and coproducing 1, 2-propylene glycol by hydrogenating 3-hydroxypropionaldehyde aqueous solution |
| CN116262683B (en) * | 2021-12-13 | 2024-11-01 | 中国科学院大连化学物理研究所 | Preparation method of 1, 3-propylene glycol |
| CN117362152B (en) * | 2023-10-09 | 2025-10-17 | 江苏扬农化工集团有限公司 | Preparation method and product of 1, 3-propylene glycol |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100432194C (en) * | 2005-10-19 | 2008-11-12 | 中国石油化工股份有限公司 | A kind of paraffin hydrorefining catalyst and its preparation method and application |
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|---|---|
| CN1428322A (en) | 2003-07-09 |
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