CN103706392A - Double-layer combined catalyst for preparing normal propyl alcohol by glycerine hydrogenation - Google Patents
Double-layer combined catalyst for preparing normal propyl alcohol by glycerine hydrogenation Download PDFInfo
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- CN103706392A CN103706392A CN201310717291.1A CN201310717291A CN103706392A CN 103706392 A CN103706392 A CN 103706392A CN 201310717291 A CN201310717291 A CN 201310717291A CN 103706392 A CN103706392 A CN 103706392A
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Abstract
The invention provides a double-layer combined catalyst for preparing normal propyl alcohol by glycerine hydrogenation. According to the combined catalyst, a microporous molecular sieve and a supported nickel catalyst are filled layer by layer and combined to use; a weight ratio of usage amount of the microporous molecular sieve to the supported nickel catalyst is (1:20)-(15:1); the catalyst combination is applied to a fixed bed reactor; a good yield of normal propyl alcohol can be acquired by taking hydrogen and a glycerine aqueous solution as raw materials; the catalyst combination is low in cost, the raw materials are easily available and the preparation process is friendly to the environment. Compared with the catalyst comprising noble metals including Pt, Ru, Rh, Ir, Re and the like, the catalyst material has the obvious cost advantages; as the catalyst consumption in the industrial application is huge, the cost advantage of the double-layer combined catalyst is prominent; compared with a monolayer catalyst comprising noble metals including Ni, Cu and the like, a prominently-improved yield of the normal propyl alcohol can be obtained due to the adoption of the double-layer combinatorial catalyst.
Description
Technical field
The present invention relates to industrial hydrogenation catalyst technical field, relate in particular to and a kind ofly at fixed bed reactors, carry out the bilayer that glycerine hydrogenation uses in producing normal propyl alcohol (Eq.1) and load catalyst combination.
Background technology
Biodiesel is that grease and methyl alcohol carry out the product after ester exchange reaction.Another product of this reaction is glycerine.Therefore, along with the development of production of biodiesel ability, how utilizing the chemical products of glycerol production high value to become one of key factor promoting biodiesel industrial competitiveness, is also one of study hotspot in new forms of energy production field.Glycerine hydrogenation being removed to part oxygen element component in its molecule, thereby produce the chemical products such as propyl alcohol, two propyl alcohol, is one of important channel of glycerine utilization.The core technology of this production process be need can high efficiency, highly selective becomes transformation of glycerol single catalyst or the combination catalyst of target product.
Fixed bed reactors are important type of reactor of glycerine hydrogenation reaction.At present for glycerine hydrogenation normal propyl alcohol processed, load the catalyst in fixed bed, its common feature is in reaction tube inner catalyst layer, only to comprise the catalyst of single kind, or the even mixing of different catalysts.That is to say, beds is single.For this reaction, also do not use at present more than one catalyst layer, layering to load combination catalyst technique.
Below that two catalyst of loading about individual layer are produced the example of normal propyl alcohol for glycerine hydrogenation.
The people such as Zhu report Pt-HSiW/ZrO
2catalyst (document: S.Zhu, Y.Zhu, S.Hao, H.Zheng, T.Mo, Y.Li, GreenChemistry, 14 (2012) 2607 – 2616.).The concrete technology condition that this catalyst obtains 80% normal propyl alcohol yield is: glycerine water solution (liquid) concentration 10wt%, liquid air speed (LHSV) is 0.045h
-1, temperature is 200 ℃, H in pressure 5Mpa, reactant
2/ glycerine mol ratio is 137:1.
The people's such as the Friedrich of foreign study group report (document: E.vanRyneveld, A.S.Mahomed, P.S.vanHeerden, M.J.Green, H.B.Friedrich, GreenChem.13 (2011) 1819 – 1827.) is used individual layer Ni/SiO
2catalyst is 3.0h in liquid air speed (LHSV)
-1, at 320 ℃ of temperature, obtaining normal propyl alcohol yield is 42.4%.
Existingly for glycerine hydrogenation, produce normal propyl alcohol catalyst and can be divided into two classes.The first kind is to take the precious metal catalyst that the metals such as platinum (Pt), ruthenium (Ru), rhodium (Rh) and rhenium (Re) are representative; Equations of The Second Kind is to take the base metal class catalyst that nickel (Ni) and copper (Cu) is representative.
Use precious metal catalyst under certain Optimization Technology, can obtain higher normal propyl alcohol yield.But its shortcoming is expensive, cannot under high liquid air speed (or matter speed) condition, obtain higher normal propyl alcohol yield simultaneously.With Pt-HSiW/ZrO
2catalyst is example, although this catalyst can obtain the normal propyl alcohol yield that surpasses 80% under certain process conditions, under this condition, liquid air speed is only 0.045h
-1; Yet air speed is increased to 0.18h
-1, glycerine yield is plummeted to 20%.Cannot high-speed (or matter speed) lower obtain high propyl alcohol yield also significant limitation its using value.
Use base metal class catalyst to be conventionally difficult to obtain higher normal propyl alcohol yield.As use above-mentioned individual layer Ni/SiO
2catalyst, propyl alcohol yield is the highest just reaches 42.4%, and obtains this yield and also need higher temperature (320 ℃).Change carrier into Al
2o
3and other condition is constant, the yield of normal propyl alcohol only has 35%.
For glycerine hydrogenation normal propyl alcohol processed, the object of the invention is at present, propose a kind of new catalyst preparation and operation that is different from single-layer catalyst system.For glycerine hydrogenation, as for normal propyl alcohol, wish do not using under the condition of expensive precious metal catalyst, obtain close with precious metal catalyst or better catalytic performance.
Summary of the invention
Inventor thinks that use layering is loaded, every layer of catalyst combination with different catalysis after in earlier stage to the research of glycerine hydrogenation deoxidation microcosmic principle, is conducive to the deep hydrogenation deoxidation of glycerine.Therefore the present invention proposes a kind of catalyst combination for fixed bed reactors.The feature of this catalyst combination can be described with Fig. 1.
In the reaction tube of Fig. 1, the acid micro porous molecular sieve of certain mass is filled in to reaction tube and forms molecular sieve catalyst layer.Then the loading type nickel-based catalyst of certain mass is contained in to the downstream (flow direction with glycerine and hydrogen is as the criterion) of molecular sieve layer.The mass ratio of the two is controlled at 1:20～15:1(molecular sieve: Raney nickel), obtain catalyst combination.Two catalyst layers all fill up the cross section that reaction tube footpath makes progress.Two catalyst layers are generally near cylindrical, but any geometry all can be used for follow-up glycerine hydrogenation reaction experiment in principle.
Obtain above-mentioned catalyst combination, need to first prepare acid microporous molecular sieve catalyst and nickel catalyst carried.After having invented above-mentioned catalyst combination, inventor has developed and this catalyst combination has been produced to the reaction process of normal propyl alcohol for glycerine hydrogenation.It should be noted that, although the preparation of above-mentioned two kinds of catalyst need to be implemented by professional and technical personnel, its independent preparation technology is not within protection scope of the present invention; For the restriction type catalyst (being defined by the claims) of this catalyst combination within protection scope of the present invention.
The technical scheme that the present invention takes is:
The double-deck combination catalyst of producing propyl alcohol for glycerine hydrogenation of the present invention is to be loaded by micro porous molecular sieve and nickel catalyst carried layering, is used in combination, and the weight proportion of micro porous molecular sieve and nickel catalyst carried consumption is 1:20-15:1.
The double-deck combination catalyst of producing propyl alcohol for glycerine hydrogenation of the present invention is loaded in fixed bed reactors; According to the flow direction of reactant, micro porous molecular sieve layer is in the upstream of nickel catalyst carried layer.
Micro porous molecular sieve is wherein any of β type, Y type, USY type, X-type, FMI type, SAPO type, MOR type, FER type, LTA type molecular sieve or their mixture.
In micro porous molecular sieve, elements Si/Al mol ratio is at 1.5-150.
The nickel catalyst carried porous carrier that used, carrier is Al
2o
3, zeolite molecular sieve, heteropoly acid, diatomite, hydrotalcite, SiO
2, MgO, TiO
2, ZrO
2, any in amorphous aluminum silicate or activated carbon or their mixture.
Nickel catalyst carried its active metal element is Ni, or Ni and other one or more metallic element combinations, but the molar fraction of Ni in all active metal elements is more than 0.6.
In nickel catalyst carried, the load capacity of element Ni is 1%-25%.
Preparation method and the evaluation method of the double-deck combination catalyst of producing propyl alcohol for glycerine hydrogenation of the present invention are as follows:
(1) preparing acid micro porous molecular sieve (is that molecular sieve cation-bit is H
+).The micro porous molecular sieve that business is bought and the ammonium salt solution of finite concentration (0.1mol/L～1mol/L) carry out mix and blend, make it that ion-exchange occur.Control 40～90 ℃ of mixed system temperature, mixing time 1～6h, turn 20～1000/min of mixing speed.Filter afterwards and obtain pressed powder, and this powder is dried, then roasting 2-8h in air at 300～600 ℃.By the molecular sieve powder compression molding obtaining, smash to pieces, sieve is got the particle of 10～100 orders (or less order is counted scope).
(2) prepare loading type nickel-based catalyst.First preparation or purchase granular size are the porous catalyst carrier of 10～100 orders (or less order is counted scope).By carrier roasting 2-8h in air at 300～600 ℃.Take 1.0g carrier, measure the water volume value (V that it can absorb
inhale).At volume, be then V
inhalewater in, the targeted loads amount according to Ni metal on carrier, calculates and adds the solubility Ni salt of respective amount, as Ni (NO
3)
2, NiSO
4deng, obtain Ni salting liquid.By carrier impregnation, in above-mentioned Ni salting liquid, proportioning is that every 1.0g carrier corresponding volume is V
inhaleni salting liquid, dipping 1h more than.Carrier after dipping is dried, then roasting 2-6h in air at 550～600 ℃.Then above-mentioned product is packed in stainless steel or crystal reaction tube, use the H of 10-50mL/min
2stream reduces 6-12h at 450-600 ℃, the black sample obtaining, i.e. loading type nickel-based catalyst.Because fragmentation or reunion may occur catalyst granules in above-mentioned processing procedure, therefore can again with sieve sieve, get the loading type nickel-based catalyst of 10～100 orders (or less order is counted scope).
(3) step (1) and (2) resulting catalyst are loaded respectively in fixed bed reactors according to mode shown in Fig. 1, obtained the catalyst combination of acid micro porous molecular sieve layer-nickel catalyst carried layer.
(4) this catalyst combination is used for to glycerine and H
2reaction.Use glycerine water solution (glycerine volume ratio is 3%～65%) and H
2as reactant, the value of controlling liquid air speed (being volume flow rate/catalyst combination cumulative volume of glycerine water solution) is 0.2h
-1～10h
-1, H
2volume flow rate be glycerine volume flow rate 10-500 doubly, H
2pressure is 0.5-5MPa.Reaction temperature is 180 ℃～230 ℃.The yield that flows out normal propyl alcohol in product can be 40%～86%.
Micro porous molecular sieve type in step (1) and the bearer type in step 2 and active metal load capacity illustrate in claims.In micro porous molecular sieve principle in step 1, also can use mesopore molecular sieve, or acid ion exchange resin replaces.
When the Ni salting liquid in step (2) configures, also can add a certain amount of other soluble metallic salt, the integral molar quantity of other salt is no more than 2/3 of Ni salt mole.Be on loading type nickel-based catalyst, also to contain a certain amount of other metal promoter.
Step (4) product analysis is sampled after reaction temperature is stablized 30min; Product adopts gas chromatographic analysis.During chromatography, use n-butanol as interior mark, no matter for reactant or product, corresponding to the glycerine in fixed amount reactant, add the internal standard compound matter of fixed amount to do quantitative reference.The computing formula of glycerol conversion yield and normal propyl alcohol yield is:
Glycerol conversion yield=1-(in product in glycerol concentration/reactant glycerol concentration) * 100%
Normal propyl alcohol yield=(in product in normal propyl alcohol concentration/reactant glycerol concentration) * 100%.
Good effect of the present invention is as follows:
Compared with only use the technology pattern of single catalyst layer in the past, the bilayer in the present invention is loaded catalyst combination, produces normal propyl alcohol new technology pattern is provided for glycerine hydrogenation.The selection of the relative consumption of molecular sieve layer and nickel-base catalyst and separately character is very flexible, is easy to control.
From principle, the double-layer catalyst combination in the present invention can also be for the hydrogenation reaction of other hydroxyl compound, as the hydrogenation reaction of glucose.
Use this double-layer catalyst combination and the nickel catalyst carried productive rate that has significantly improved normal propyl alcohol of comparing that only uses individual layer.For example in background technology, improve and use individual layer Ni/SiO
2catalyst is 3.0h at 320 ℃, liquid air speed
-1under condition, can obtain～42% normal propyl alcohol yield, and molecular sieve+Ni/SiO
2catalyst combination can under 220 ℃, same liquid air speed, obtain the normal propyl alcohol yield up to 86%.
The normal propyl alcohol yield that catalyst combination in use the present invention obtains is no less than using precious metal catalyst, and catalysis material used in the present invention belongs to cheap material, so it has obvious cost advantage.
Accompanying drawing explanation
Fig. 1 be double-deck combination catalyst of the present invention loading method with and for the schematic diagram of reaction test.
The specific embodiment
The following examples are to describe in further detail of the present invention.
Embodiment 1
First by Si/Al than being 15 beta-molecular sieve and the NH of 0.2mol/L
4nO
3the aqueous solution carries out three secondary ion exchanges according to the method for step (1) and obtains acidic beta molecular sieve (H β).With Ni (NO
3)
2for Ni source, with porous Al
2o
3for carrier is prepared Al according to the method for step (2)
2o
3ni catalyst (the Ni/Al of load
2o
3).Above-mentioned two kinds of catalysis materials are sieved and retain 30-80 order part.In the stainless steel fixed bed reactors that are 5mm at internal diameter, minute above-mentioned two kinds of catalysis materials of two-layer filling, obtain catalyst combination.In this combination, H β layer is in Ni/Al
2o
3the upstream of layer, the weight of the two is respectively 0.6g and 1.2g.
The process conditions of glycerine hydrogenation reaction are: reactant is that flow velocity is the 25%(volume ratio of 0.2mL/min) glycerine water solution and the flow velocity H that is 100mL/min
2; Flow velocity rises to 225 ℃ by catalyst layer temperature after reaching and stablizing; Reaction pressure is 2MPa.Product is used the refrigerant of-6～-1 ℃ cooling, and analyzes with Agilent6890 type gas chromatograph.
The glycerol conversion yield that embodiment 1 obtains is after testing 99%, and normal propyl alcohol yield is 65%.
Embodiment 2
Method is with embodiment 1, and difference is for to change the use amount of H β into 1g.The glycerol conversion yield that embodiment 2 obtains is after testing 100%, and normal propyl alcohol yield is 72%.
Embodiment 3
Method is with embodiment 2, and difference is for to change beta-molecular sieve into ZSM-5 molecular sieve.The glycerol conversion yield that embodiment 3 obtains is after testing 77%, and normal propyl alcohol yield is 52%.
Although illustrated and described embodiments of the invention, for the ordinary skill in the art, be appreciated that without departing from the principles and spirit of the present invention and can carry out multiple variation, modification, replacement and modification to these embodiment, scope of the present invention is limited by claims and equivalent thereof.
Claims (7)
1. a double-deck combination catalyst of producing normal propyl alcohol for glycerine hydrogenation, it is characterized in that: this combination catalyst is to be loaded by micro porous molecular sieve and nickel catalyst carried layering, be used in combination, the weight proportion of micro porous molecular sieve and nickel catalyst carried consumption is 1:20-15:1.
2. combination catalyst as claimed in claim 1, is characterized in that: load in fixed bed reactors; According to the flow direction of reactant, micro porous molecular sieve layer is in the upstream of nickel catalyst carried layer.
3. described combination catalyst as claimed in claim 1, is characterized in that: micro porous molecular sieve is wherein any of β type, Y type, USY type, X-type, FMI type, SAPO type, MOR type, FER type, LTA type molecular sieve or their mixture.
4. micro porous molecular sieve as claimed in claim 3, is characterized in that: in micro porous molecular sieve, elements Si/Al mol ratio is at 1.5-150.
5. described combination catalyst as claimed in claim 1, is characterized in that: the nickel catalyst carried porous carrier that used, carrier is Al
2o
3, zeolite molecular sieve, heteropoly acid, diatomite, hydrotalcite, SiO
2, MgO, TiO
2, ZrO
2, any in amorphous aluminum silicate or activated carbon or their mixture.
6. described combination catalyst as claimed in claim 1, it is characterized in that: nickel catalyst carried its active metal element is Ni, or Ni and other one or more metallic element combinations, but the molar fraction of Ni in all active metal elements is more than 0.6.
7. described combination catalyst as claimed in claim 1, is characterized in that: in nickel catalyst carried, the load capacity of element Ni is 1%-25%.
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| CN201310717291.1A CN103706392B (en) | 2013-12-23 | 2013-12-23 | Double-layer combined catalyst for preparing normal propyl alcohol by glycerine hydrogenation |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AT520954A1 (en) * | 2018-02-28 | 2019-09-15 | Omv Refining & Marketing Gmbh | Process and apparatus for the catalytic conversion of a mixture of substances |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6391815B1 (en) * | 2000-01-18 | 2002-05-21 | Süd-Chemie Inc. | Combination sulphur adsorbent and hydrogenation catalyst for edible oils |
| US20070043250A1 (en) * | 2005-08-18 | 2007-02-22 | Teng Xu | Catalytic conversion of oxygenates to olefins |
| 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 |
-
2013
- 2013-12-23 CN CN201310717291.1A patent/CN103706392B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6391815B1 (en) * | 2000-01-18 | 2002-05-21 | Süd-Chemie Inc. | Combination sulphur adsorbent and hydrogenation catalyst for edible oils |
| US20070043250A1 (en) * | 2005-08-18 | 2007-02-22 | Teng Xu | Catalytic conversion of oxygenates to olefins |
| 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 |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AT520954A1 (en) * | 2018-02-28 | 2019-09-15 | Omv Refining & Marketing Gmbh | Process and apparatus for the catalytic conversion of a mixture of substances |
| CN112135810A (en) * | 2018-02-28 | 2020-12-25 | Omv下游有限公司 | Process for the catalytic conversion of glycerol to propanol alcohols |
| US11512032B2 (en) | 2018-02-28 | 2022-11-29 | OMV Downstream GmbH | Method and device for the catalytic conversion of a substance mixture |
| AT520954B1 (en) * | 2018-02-28 | 2024-02-15 | Omv Refining & Marketing Gmbh | Process and device for the catalytic conversion of a mixture of substances |
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