CN105709778A - Catalyst for catalytic hydrogenation of 3-hydroxyl propionaldehyde to prepare 1,3-propylene glycol, preparation method and applications thereof - Google Patents
Catalyst for catalytic hydrogenation of 3-hydroxyl propionaldehyde to prepare 1,3-propylene glycol, preparation method and applications thereof Download PDFInfo
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Abstract
The invention relates to a catalyst for catalytic hydrogenation of 3-hydroxyl propionaldehyde to prepare 1,3-propylene glycol. The catalyst comprises a carrier (A) and active components: Ni, Rh, and metal (X), and is named as Ni-Rh-X/A catalyst for short; wherein the active component (X) is one or more of rhenium, tungsten, chromium, lanthanum, iron, molybdenum, and cobalt; and the carrier (A) is one or more of silicon dioxide, alumina, magnesium oxide, titanium dioxide, and activated clay. In the presence of the provided catalyst, a water solution of 3-hydroxyl propionaldehyde can be converted into 1,3-propylene glycol through two-section hydrogenation reactions. Precious metal (Rh) is added to effectively reduce the reaction pressure; in the second section, an acidic catalyst is added to improve the selectivity of 1,3-propylene glycol, the problems of conventional methods are solved therefore, the production cost is reduced, and the benefits are increased.
Description
Technical field
The present invention relates to a kind of 3-HPA catalytic hydrogenation and prepare the process of 1,3-PD, more particularly relate to a kind of 3-HPA aqueous solution and be converted into the process of 1,3-PD by secondary hydrogenation.
Background technology
1,3-PD is a kind of important Organic Chemicals, is widely used in the synthesis of plasticizer, detergent, preservative, emulsifying agent, polyester and polyurethane, it is possible to as antifreezing agent, solvent and protective agent etc..Most important of which is to prepare poly terephthalic acid 1,3-PD ester (PPT).PPT is the polyester material of a kind of excellent performance, have high-performance and the poly terephthalic acid 1 of polyethylene terephthalate concurrently, the workability of 4-butanediol ester, there is again good resilience and the antifouling property of nylon, and it is easy coloring, wear-resisting, fully develop talents in fields such as carpet, engineering plastics, garment materials, have a extensive future, be the focus of current fiber synthesis exploitation.At present by Hydroformylation of Ethylene Oxide For 3-hydroxypropanal Synthesis, it is the most successful production route again through Hydrogenation for 1,3-PD.It can be seen that 3-HPA Hydrogenation is divided into for the catalyst of 1,3-PD existing patent: (1) Raney nickel-base catalyst；(2) platinum, palladium or ruthenium are the loaded catalyst of active component；(3) loaded catalyst being active component with nickel.
Chinese patent CN1122568 carries out 3-HPA interval Hydrogenation for 1 with the Raney nickel-base catalyst that Cr, Zn, Mo, Fe or Cr+Fe modify, ammediol, at 3.0-10.0MPa pressure, reaction 1h under 50 degree, then hydrogenation under 125-130 degree again, 1, the yield of ammediol is 100%, but catalyst is powder body, post catalyst reaction and reactant liquor separation difficulty；And be batch tank reaction, it is difficult to large-scale commercial Application.Patent CN1428322 adopts Ni-A type catalyst, is reacted by two-stage hydrogenation, by 3-HPA Hydrogenation for 1, ammediol, wherein catalyst A is any in Cr, Zn, Mo or Fe, and the conversion ratio of 3-HPA is 100%, but the poor stability of catalyst.Shell patent CN132847A adopts the nickel-base catalyst of Ni-Mo-A, carrier A is oxide or the metal-oxide of silicon, at 10-15MPa pressure, the two-stage hydrogenation of 50-60 DEG C/110-130 DEG C, the conversion ratio of 3-HPA is 100%, and 1,3-PD selectivity is 90%, owing to generating the by-product of acetals, reduce the selectivity of PDO.
At home and abroad, by 3-HPA Hydrogenation in the patent of 1,3-PD, with nickel for the reaction pressure needed for the catalyst of active component higher than 7MPa, in the technological process of shell, reaction pressure 10-15MPa, add difficulty and production cost.Shell, in patent CN101583242A, adopts Ni-Mo-Ru-Al2O3Multicomponent catalyst, under 6.89-11MPa pressure, by 50-100 DEG C/120-190 DEG C two-stage hydrogenation, the conversion ratio of 3-HPA is 100%, the selectivity of 1,3-PD > 90%, the reaction pressure needed for hydrogenation reaction is lower than the nickel-base catalyst without noble metal, but needing higher reaction condition, reaction condition is still relatively high.
Summary of the invention
Present invention aims to current 3-HPA Hydrogenation for 1, the defect of ammediol technique, it is provided that a kind of support type multicomponent catalyst and preparation method, under this catalysts conditions, 3-HPA aqueous solution is converted into 1,3-PD by secondary hydrogenation reaction.This catalyst adds noble metal Rh, effectively reduces reaction pressure；Add acidic catalyst at second segment, improve the selectivity of 1,3-PD, thus solving prior art Problems existing, reducing production cost, increasing the benefit.
The present invention is achieved by the following technical solutions:
A kind of 3-HPA Hydrogenation is for 1,3-PD catalyst, including carrier A and active component: Ni, Rh and metal X；Referred to as Ni-Rh-X/A catalyst；Wherein, active component X is the combination of any one or more in rhenium, tungsten, chromium, lanthanum, ferrum, molybdenum or cobalt；Carrier A is the mixture of any one or more in silicon dioxide, aluminium oxide, magnesium oxide, titanium dioxide or active hargil.
Preferably, described active component X is selected from rhenium, molybdenum, cobalt and lanthanum.
Preferably, described carrier A is selected from silicon dioxide, aluminium sesquioxide and titanium dioxide.Described aluminium sesquioxide preferred γ-Al2O3。
Preferably, in described catalyst, the weight/mass percentage composition of nickel is 1-20wt%, it is preferred to 5-15wt%.
Preferably, in described catalyst, the weight/mass percentage composition 0.1-10wt% of rhodium, it is preferred to 0.1-1wt%.
Preferably, in described catalyst, the weight/mass percentage composition 0.1-10wt% of component X, it is preferred to 3-5wt%.
Preferably, in described catalyst, the weight/mass percentage composition 60-90wt% of carrier A, it is preferred to 70-90wt%.
The preparation of described catalyst can adopt infusion process or mixing method:
Adopt infusion process to prepare described 3-HPA Hydrogenation for 1,3-PD catalyst, comprise the following steps:
(1) soluble salt solution of the soluble salt solution of nickel, the soluble salt solution of rhodium and auxiliary agent X is prepared respectively；
(2) by metering, take carrier and be placed in the soluble salt solution of nickel and carry out incipient impregnation load, then dry, roasting, for next step after cooling；
(3) by metering, the carrier after step (2) being lowered the temperature is placed in the soluble salt solution of rhodium and carries out incipient impregnation load, then dry, roasting, for next step after cooling；
(4) by metering, the carrier after step (3) being lowered the temperature is placed in the soluble salt solution of auxiliary agent X and carries out incipient impregnation load, and then dry, roasting, lowers the temperature and get final product；
Wherein,
Preferably, the soluble salt of described nickel is selected from nickel nitrate.
Preferably, the soluble salt of described rhodium is selected from rhodium nitrate.
Preferably, the soluble salt of described auxiliary agent X is selected from the nitrate of auxiliary agent X, acetate and ammonium salt etc..
Preferably, in step (1), the concentration of the soluble salt solution of described nickel is 10-20wt%.
Preferably, in step (1), the concentration of the soluble salt solution of described rhodium is 1-3wt%.
Preferably, in step (1), in the soluble salt solution of described auxiliary agent X, the concentration of slaine is 2-5wt%.
Pressing metering ratio under load request, described incipient impregnation load, when namely impregnating, make liquor capacity equal with the saturated water adsorptive value of carrier every time；The concentration of each solution is not necessarily to equal, it is preferable that under condition, as long as meeting in above-mentioned concentration range, then passing through repeatedly dipping and reaching the load capacity of metering ratio.
Preferably, in step (2), described dipping process carries out under 40-80 DEG C of water bath condition, impregnates 3-5h.
Preferably, in step (2), described dry employing temperature programming, heating rate 0.5-3 DEG C/min, then at 90-110 DEG C, dry 2-6h.
Preferably, in step (2), described roasting adopts temperature programming, heating rate 0.5-3 DEG C/min, then roasting 4-8h in air atmosphere at 400-500 DEG C.
Preferably, in step (3), described dipping process carries out under 40-80 DEG C of water bath condition, impregnates 3-5h.
Preferably, in step (3), described dry temperature is 90-110 DEG C, dry 2-6h.
Preferably, in step (3), described roasting adopts temperature programming, heating rate 0.5-3 DEG C/min, then roasting 4-8h in air atmosphere at 400-500 DEG C.
Preferably, in step (4), described dipping process carries out under 40-80 DEG C of water bath condition, impregnates 3-5h.
Preferably, in step (4), described dry temperature is 90-110 DEG C, dry 2-6h.
Preferably, in step (4), described roasting adopts temperature programming, heating rate 0.5-3 DEG C/min, then roasting 4-8h in air atmosphere at 400-500 DEG C.
Adopt mixing method to prepare described 3-HPA Hydrogenation for 1,3-PD catalyst, comprise the following steps:
(I) weigh nickel oxide, rhodium oxide, the oxide of auxiliary agent X and carrier by metering, add in kneader and be sufficiently mixed；
(II) binding agent and structural promoter it are subsequently adding, extruded moulding after kneading；
(III) dried, roasting, then lower the temperature and both obtain；
Wherein,
Preferably, in step (II), described binding agent is selected from dust technology (concentration 10-20wt%), citric acid, Ludox etc..
Preferably, in step (II), described structural promoter is selected from Polyethylene Glycol (degree of polymerization is 300-4000), cellulose, polyvinyl alcohol (degree of polymerization is 300-4000).
Preferably, the addition of described binding agent is the 2-6wt% of the dry powder gross weight of the oxide of nickel, the oxide of rhodium, the oxide of auxiliary agent X and carrier.
Preferably, the addition of described structural promoter is the 2-5wt% of the dry powder gross weight of the oxide of nickel, the oxide of rhodium, the oxide of auxiliary agent X and carrier.
Preferably, in step (II), the speed of described kneading is 20-60rpm, mediates stirring 4-8h.
Preferably, in step (II), described extruded moulding, cut into 3-10mm.
Preferably, in step (III), described dry temperature is 90-110 DEG C, dry 2-6h.
Preferably, in step (III), at the temperature of described roasting is 400-500 DEG C, roasting 4-8h in air atmosphere.
Described catalyst before use, at H2: N2Volume ratio be 1:1-1:2 gaseous mixture in reduce, it is preferable that reducing condition: reduction pressure 0.1-0.5MPa, gas space velocity 1000-1500h-1, reduction temperature is 300-400 DEG C, and the recovery time is 30-40h.
A kind of 3-HPA Hydrogenation is for the process of 1,3-PD, with the aqueous solution of 3-HPA and hydrogen for raw material, under the catalytic action of Above-mentioned catalytic agent, adopts the secondary hydrogenation synthesis 1,3-PD of series connection.
Preferably, aforementioned Ni-Rh-X/A catalyst loads in the first hydrogenation workshop section；The mixed catalyst of aforementioned Ni-Rh-X/A catalyst and acidic catalyst loads in second hydrogenation workshop section.
Preferably, described Ni-Rh-X/A catalyst is 1:1-3:1 at the first filling mass ratio being hydrogenated with workshop section and the second hydrogenation workshop section.
Preferably, the first reaction temperature 40-80 DEG C of workshop section of hydrogenation, it is preferred to 45-65 DEG C.
Preferably, Ni-Rh-X/A catalyst described in the second hydrogenation workshop section and acidic catalyst mix for 5:1-8:1 in mass ratio.
Preferably, described acidic catalyst is selected from sulfonic acid ion exchange resin and acid zeolite.
Preferably, the second reaction temperature 80-130 DEG C of workshop section of hydrogenation, more preferably 100-130 DEG C.
Preferably, first it is hydrogenated with workshop section, the second hydrogenation workshop section hydrogenation reaction pressure 3-10MPa, more preferably 3-5MPa.
Preferably, the concentration of aqueous solution of described 3-HPA is 5-20wt%, it is preferred to 5-10wt%.
Preferably, the air speed of the aqueous solution of described 3-HPA is 5-15h-1, more preferably 5-10h-1。
Preferably, hydrogen is 2:1-20:1 with the mol ratio of 3-HPA, more preferably 5:1-10:1.
The technique effect that the present invention obtains: by adding the auxiliary agent such as noble metal Rh and La or Re or Mo in nickel-base catalyst, preparation is used for synthesizing 1, the catalyst of ammediol, and for 3-HPA Hydrogenation for 1, in ammediol two-stage hydrogenation technique, effectively reduce the reaction pressure in course of reaction；It is hydrogenated with section addition acidic catalyst second simultaneously and improves the selectivity of 1,3-PD.
Detailed description of the invention
Below by way of specific instantiation, technical scheme is described.Should be understood that one or more method steps that the present invention mentions do not repel before and after described combination step, there is also additive method step or additive method step can also be inserted between these steps specifically mentioned；Should also be understood that these embodiments are merely to illustrate the present invention rather than restriction the scope of the present invention.And, except as otherwise noted, the numbering of various method steps is only the convenient tool differentiating various method steps, but not for limiting the ordering of various method steps or limiting the enforceable scope of the present invention, the change of its relativeness or adjustment, when changing technology contents without essence, when being also considered as the enforceable category of the present invention.
Embodiment 1-7 adopts infusion process to prepare 3-HPA Hydrogenation for 1,3-PD catalyst:
(1) prepare the aqueous solution of the soluble-salt of the component X of the nickel nitrate aqueous solution of 15wt%, the rhodium nitrate aqueous solution of 3wt% and 4wt% respectively, be deionized water with water；
(2) by metering, weigh alumina globule as carrier, adopt equi-volume impregnating by carrier impregnation in nickel nitrate aqueous solution, at 60 DEG C of temperature of water-bath, impregnate 4h；
(3) under 0.8 DEG C/min programmed rate, then it is warming up at 100 DEG C dry 4h, continues 0.8 DEG C/min temperature programming to roasting 6h at 450 DEG C；
(4) then according to the processing procedure of step (2) and (3), load rhodium and auxiliary agent X are distinguished；
Reduction pretreatment: load reactor after roasting, be 0.2MPa, H at pressure2/N2The gaseous mixture of=1:2 volume ratio, temperature is 360 DEG C of reduction 36h, and reduction adjusts, after terminating, the condition that reaction is required.
Catalyst composition in embodiment 1-7, as shown in table 1.
Embodiment 8-14 adopts mixing method to prepare 3-HPA Hydrogenation for 1,3-PD catalyst:
(1) by metering than weighing nickel oxide, rhodium oxide, the oxide of auxiliary agent X and carrier, join in kneader, be sufficiently mixed；
(2) add concentration be 15wt% dust technology as binding agent, consumption is the 5wt% of dry powder, add Polyethylene Glycol (degree of polymerization 3000) be structural promoter, consumption is the 4wt% of dry powder；
(3) mediating speed is 20rpm, mediates 4h；
(4) mediate mix homogeneously extruded moulding, be cut into 5mm；
(5) at 100 DEG C, 4h, roasting 6h at 450 DEG C are then dried.
Reduction pretreatment: load reactor after roasting, be 0.2MPa, H at pressure2: N2The gaseous mixture of=1:2, temperature is 360 DEG C of reduction 36h, and reduction adjusts, after terminating, the condition that reaction is required.
Catalyst composition in embodiment 8-14, as shown in table 2.
The composition of table 1 embodiment 1-7 catalyst
The composition of table 2 embodiment 8-14 catalyst
2 catalyst activity evaluations:
Freshly prepd catalyst is respectively charged in the first paragraph of series connection and the reactor of the fixing bed shell and tube of second segment, the filling mass ratio of the multicomponent catalyst of first paragraph and second segment Ni-Rh-X/A support type is 3:1, and second segment is that 1:8 adds sulfonic acid ion exchange resin by the mass ratio with the multicomponent catalyst of Ni-Rh-X/A support type.The 3-HPA aqueous solution of raw material 8wt% and H2Enter reactor after preheating, and at second segment reactor sample analysis, calculate reaction conversion ratio and selectivity.The reaction condition of embodiment and result such as table 3.
The amount (mole) * 100% of the 3-HPA of conversion ratio=(amount (mole) of the remaining 3-HPA of 1-)/entrance reactor；
The amount (mole) * 100% of the 3-HPA that amount (mole)/reaction of the 3-HPA that the 1,3-propylene glycol conversion of selectivity=generation consumes converts；
Table 3 evaluating catalyst condition and result
Embodiment 15
Hydrogenation catalyst in the embodiment 3 prepared loads the two reactor of series connection, two reactor filling mass ratio 3:1, and second segment is that 1:8 adds sulfonic acid ion exchange resin by the mass ratio with the multicomponent catalyst of Ni-Rh-X/A support type.At 360 DEG C, reduction 36h, is cooled to 55 DEG C after reduction.The 3-HPA aqueous solution of material concentration 8wt% and H2Reactor is entered, reaction condition: first paragraph reaction temperature 55 DEG C after preheated, second segment reaction temperature 110 DEG C, 3-HPA aqueous solution hourly space velocity 8h-1, H2: 3-HPA mol ratio is 6:1, reaction pressure 4MPa, and through the reaction of 300h, the conversion ratio 99.9%, 1 of 3-HPA, the selectivity of 3-PDO is 95%.This embodiment illustrates that catalyst of the present invention has longer service life.
Claims (13)
1. 3-HPA Hydrogenation is for a 1,3-PD catalyst, including carrier A and active component: Ni, Rh and metal X；Referred to as Ni-Rh-X/A catalyst；Wherein, active component X is the combination of any one or more in rhenium, tungsten, chromium, lanthanum, ferrum, molybdenum or cobalt；Carrier A is the mixture of any one or more in silicon dioxide, aluminium oxide, magnesium oxide, titanium dioxide or active hargil.
2. a kind of 3-HPA Hydrogenation as claimed in claim 1 is for 1, ammediol catalyst, it is characterized in that, in described catalyst, the weight/mass percentage composition of nickel is 1-20wt%, the weight/mass percentage composition 0.1-10wt% of the weight/mass percentage composition 0.1-10wt%, component X of rhodium, the weight/mass percentage composition of carrier A is 60-90wt%.
3. a kind of 3-HPA Hydrogenation as claimed in claim 2 is for 1, ammediol catalyst, it is characterized in that, in described catalyst, the weight/mass percentage composition of nickel is 5-15wt%, the weight/mass percentage composition 3-5wt% of the weight/mass percentage composition 0.1-1wt%, component X of rhodium, the weight/mass percentage composition of carrier A is 70-90wt%.
4. a kind of 3-HPA Hydrogenation as described in as arbitrary in claim 1-3 is for the preparation method of 1,3-PD catalyst, for infusion process, specifically includes following steps:
(1) soluble salt solution of the soluble salt solution of nickel, the soluble salt solution of rhodium and auxiliary agent X is prepared respectively；
(2) by metering, take carrier and be placed in the soluble salt solution of nickel and carry out incipient impregnation load, then dry, roasting,
For next step after cooling；
(3) by metering, the carrier after step (2) being lowered the temperature is placed in the soluble salt solution of rhodium and carries out incipient impregnation load, then dry, roasting, for next step after cooling；
(4) by metering, the carrier after step (3) being lowered the temperature is placed in the soluble salt solution of auxiliary agent X and carries out incipient impregnation load, and then dry, roasting, lowers the temperature and get final product.
5. preparation method as claimed in claim 4, it is characterised in that also include any one in following characteristics or multinomial:
A the soluble salt of () described nickel is selected from nickel nitrate, the concentration of the soluble salt solution of described nickel is 10-20wt%；
B the soluble salt of () described rhodium is selected from rhodium nitrate, the concentration of the soluble salt solution of described rhodium is 1-3wt%；
C in the soluble salt solution of () described auxiliary agent X, the concentration of slaine is 2-5wt%；
D, in () step (2), described dipping process carries out under 40-80 DEG C of water bath condition, impregnate 3-5h；In step (2), described dry employing temperature programming, heating rate 0.5-3 DEG C/min, then at 90-110 DEG C, dry 2-6h；Described roasting adopts temperature programming, heating rate 0.5-3 DEG C/min, then roasting 4-8h in air atmosphere at 400-500 DEG C；
E, in () step (3), described dipping process carries out under 40-80 DEG C of water bath condition, impregnate 3-5h；In step (2), described dry employing temperature programming, heating rate 0.5-3 DEG C/min, then at 90-110 DEG C, dry 2-6h；Institute
State roasting and adopt temperature programming, heating rate 0.5-3 DEG C/min, then roasting 4-8h in air atmosphere at 400-500 DEG C；
F, in () step (4), described dipping process carries out under 40-80 DEG C of water bath condition, impregnate 3-5h；In step (2), described dry employing temperature programming, heating rate 0.5-3 DEG C/min, then at 90-110 DEG C, dry 2-6h；Described roasting adopts temperature programming, heating rate 0.5-3 DEG C/min, then roasting 4-8h in air atmosphere at 400-500 DEG C.
6. a kind of 3-HPA Hydrogenation as described in as arbitrary in claim 1-3 is for the preparation method of 1,3-PD catalyst, for mixing method, specifically includes following steps:
(I) weigh nickel oxide, rhodium oxide, the oxide of auxiliary agent X and carrier by metering, add in kneader and be sufficiently mixed；
(II) binding agent and structural promoter it are subsequently adding, extruded moulding after kneading；
(III) dried, roasting, then lower the temperature and both obtain.
7. preparation method as claimed in claim 6, it is characterised in that also include any one in following characteristics or multinomial:
A, in () step (II), described binding agent is selected from dust technology, citric acid and Ludox；
B, in () step (II), described structural promoter is selected from Polyethylene Glycol, cellulose, polyvinyl alcohol；
C the addition of () described binding agent is the 2-6wt% of the dry powder gross weight of the oxide of nickel, the oxide of rhodium, the oxide of auxiliary agent X and carrier；
D the addition of () described structural promoter is the 2-5wt% of the dry powder gross weight of the oxide of nickel, the oxide of rhodium, the oxide of auxiliary agent X and carrier；
E, in () step (II), the speed of described kneading is 20-60rpm, mediate stirring 4-8h；
F () described extruded moulding, cuts into 3-10mm；
G, in () step (III), described dry temperature is 90-110 DEG C, dry 2-6h；At the temperature of described roasting is 400-500 DEG C, roasting 4-8h in air atmosphere.
8. a kind of 3-HPA Hydrogenation as described in as arbitrary in right 1-3 is for the application of 1,3-PD catalyst, it is characterised in that described catalyst before use, at H2: N2Volume ratio be 1:1-1:2 gaseous mixture in reduce, reduce pressure 0.1-0.5MPa, gas space velocity 1000-1500h-1, reduction temperature is 300-400 DEG C, and the recovery time is 30-40h.
9. a 3-HPA Hydrogenation is for the process of 1,3-PD, it is characterised in that, with the aqueous solution of 3-HPA and hydrogen for raw material, under the catalytic action of the arbitrary described Ni-Rh-X/A catalyst of claim 1-3, adopt the secondary hydrogenation synthesis 1,3-PD of series connection.
10. a kind of 3-HPA Hydrogenation as claimed in claim 9 is for the process of 1,3-PD, it is characterised in that the first hydrogenation workshop section arbitrary described Ni-Rh-X/A catalyst of filling claim 1-3；The mixed catalyst of the second hydrogenation workshop section filling arbitrary described Ni-Rh-X/A catalyst of claim 1-3 and acidic catalyst.
11. a kind of 3-HPA Hydrogenation as claimed in claim 10 is for the process of 1,3-PD, it is characterised in that described Ni-Rh-X/A catalyst is 1:1-3:1 at the first filling mass ratio being hydrogenated with workshop section and the second hydrogenation workshop section；Described in second hydrogenation workshop section, the mass ratio of Ni-Rh-X/A catalyst and acidic catalyst is 5:1-8:1.
12. a kind of 3-HPA Hydrogenation as claimed in claim 11 is for the process of 1,3-PD, it is characterised in that described acidic catalyst is selected from sulfonic acid ion exchange resin and acid zeolite.
13. a kind of 3-HPA Hydrogenation as claimed in claim 9 is for the process of 1,3-PD, it is characterised in that also include any one in following characteristics or multinomial:
A the concentration of aqueous solution of () described 3-HPA is 5-20wt%；
B the air speed of the aqueous solution of () described 3-HPA is 5-15h-1；
C the mol ratio of () hydrogen and 3-HPA is 2:1-20:1；
(d) first reaction temperature 40-80 DEG C of workshop section of hydrogenation；
(e) second reaction temperature 80-130 DEG C of workshop section of hydrogenation；
(f) first hydrogenation workshop section, the second hydrogenation workshop section hydrogenation reaction pressure 3-10MPa.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN110386856A (en) * | 2018-04-19 | 2019-10-29 | 万华化学集团股份有限公司 | A kind of method that acrolein hydration adds hydrogen to prepare 1,3- propylene glycol |
| CN112264038A (en) * | 2020-11-11 | 2021-01-26 | 中国科学院宁波材料技术与工程研究所 | Noble metal loaded eggshell type catalyst and preparation method and application thereof |
| CN112457158A (en) * | 2020-11-10 | 2021-03-09 | 中国石油化工股份有限公司 | Catalyst for catalyzing hydrogenation of 3-hydroxypropionaldehyde and preparation method thereof |
| CN114011432A (en) * | 2021-12-12 | 2022-02-08 | 宁波环洋新材料股份有限公司 | 3-hydroxy propionaldehyde hydrogenation catalyst, preparation method and application thereof |
| CN114100615A (en) * | 2020-08-31 | 2022-03-01 | 中国石油化工股份有限公司 | Selective hydrogenation catalyst for four carbon fractions and preparation method thereof |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1733667A (en) * | 2005-08-29 | 2006-02-15 | 上海华谊丙烯酸有限公司 | Method for 3- hydroxyl propionaldehyde hydrogenation to produce 1,3-propanediol |
| CN1810371A (en) * | 2006-02-28 | 2006-08-02 | 上海华谊丙烯酸有限公司 | Catalyst for hydrogenating 3-hydroxy propaldehyde to prepare 1, 3-propylene glycol |
| CN101054339A (en) * | 2007-05-31 | 2007-10-17 | 上海华谊丙烯酸有限公司 | Process for preparing n-propanol by hydrogenating glycerol |
| WO2008040175A1 (en) * | 2006-09-20 | 2008-04-10 | China Petroleum & Chemical Corporation | A nickel catalyst for selective hydrogenation |
| CN101239892A (en) * | 2008-03-10 | 2008-08-13 | 上海华谊丙烯酸有限公司 | Method for preparing iso-butyraldehyde and isobutyl alcohol by methylacrolein hydrogenation |
| CN101239888A (en) * | 2008-03-10 | 2008-08-13 | 上海华谊丙烯酸有限公司 | Method for preparing isobutyl alcohol by methylacrolein hydrogenation |
-
2014
- 2014-12-05 CN CN201410737413.8A patent/CN105709778B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1733667A (en) * | 2005-08-29 | 2006-02-15 | 上海华谊丙烯酸有限公司 | Method for 3- hydroxyl propionaldehyde hydrogenation to produce 1,3-propanediol |
| CN1810371A (en) * | 2006-02-28 | 2006-08-02 | 上海华谊丙烯酸有限公司 | Catalyst for hydrogenating 3-hydroxy propaldehyde to prepare 1, 3-propylene glycol |
| WO2008040175A1 (en) * | 2006-09-20 | 2008-04-10 | China Petroleum & Chemical Corporation | A nickel catalyst for selective hydrogenation |
| CN101054339A (en) * | 2007-05-31 | 2007-10-17 | 上海华谊丙烯酸有限公司 | Process for preparing n-propanol by hydrogenating glycerol |
| CN101239892A (en) * | 2008-03-10 | 2008-08-13 | 上海华谊丙烯酸有限公司 | Method for preparing iso-butyraldehyde and isobutyl alcohol by methylacrolein hydrogenation |
| CN101239888A (en) * | 2008-03-10 | 2008-08-13 | 上海华谊丙烯酸有限公司 | Method for preparing isobutyl alcohol by methylacrolein hydrogenation |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN110386856A (en) * | 2018-04-19 | 2019-10-29 | 万华化学集团股份有限公司 | A kind of method that acrolein hydration adds hydrogen to prepare 1,3- propylene glycol |
| CN110386856B (en) * | 2018-04-19 | 2022-08-05 | 万华化学集团股份有限公司 | Method for preparing 1, 3-propylene glycol by hydration and hydrogenation of acrolein |
| CN114100615A (en) * | 2020-08-31 | 2022-03-01 | 中国石油化工股份有限公司 | Selective hydrogenation catalyst for four carbon fractions and preparation method thereof |
| CN114100615B (en) * | 2020-08-31 | 2023-08-11 | 中国石油化工股份有限公司 | Catalyst for selective hydrogenation of carbon four fraction and preparation method thereof |
| CN112457158A (en) * | 2020-11-10 | 2021-03-09 | 中国石油化工股份有限公司 | Catalyst for catalyzing hydrogenation of 3-hydroxypropionaldehyde and preparation method thereof |
| CN112457158B (en) * | 2020-11-10 | 2022-09-13 | 中国石油化工股份有限公司 | Catalyst for catalyzing hydrogenation of 3-hydroxypropionaldehyde and preparation method thereof |
| CN112264038A (en) * | 2020-11-11 | 2021-01-26 | 中国科学院宁波材料技术与工程研究所 | Noble metal loaded eggshell type catalyst and preparation method and application thereof |
| WO2022099488A1 (en) * | 2020-11-11 | 2022-05-19 | 中国科学院宁波材料技术与工程研究所 | Precious metal-loaded eggshell type catalyst, preparation method therefor, and application thereof |
| CN114011432A (en) * | 2021-12-12 | 2022-02-08 | 宁波环洋新材料股份有限公司 | 3-hydroxy propionaldehyde hydrogenation catalyst, preparation method and application thereof |
| CN114011432B (en) * | 2021-12-12 | 2024-02-02 | 宁波环洋新材料股份有限公司 | 3-hydroxy propanal hydrogenation catalyst and its preparation method and use |
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