CN106607044A - Catalyst and method for preparing 1, 6-hexanediol by hydrogenation of dialkyl 1, 6-adipate - Google Patents
Catalyst and method for preparing 1, 6-hexanediol by hydrogenation of dialkyl 1, 6-adipate Download PDFInfo
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Abstract
The invention relates to a catalyst and method for preparing 1, 6-hexanediol by hydrogenation of dialkyl 1, 6-adipate. The catalyst comprises, by weight, a) 20 to 50 parts of metallic copper or an oxide thereof, b) 30 to 60 parts of metal zinc or an oxide thereof, c) 1 to 20 parts of at least one transition metal or its oxide, and d) 1 to 20 parts of alumina. The desired alumina precursor has a specific surface area of 50 to 500m<2>/g and a total pore volume of 0.3 to 2.0ml/g. The volume of pores having diameters less than 20nm is 40-80% total pore volume. The volume of pores having diameters of 20-90nm is 10-40% total pore volume. The volume of pores having diameters greater than 90nm is 0-16% total pore volume. The catalyst can be used in the industrial production of 1, 6-hexanediol by hydrogenation of dialkyl 1, 6-adipate.
Description
Technical field
The invention belongs to field of catalytic chemistry, more particularly to one kind 1,6- hexanedioic acid dialkyl esters Hydrogenation is for 1,6- hexanediol
Catalyst and method.
Background technology
1,6- hexanediol is a kind of important fine chemical material, rise mainly for the production of high-quality polyurethane elastomer resins,
Polyester type plasticizer, ultraviolet-curing paint, Merlon, medicine intermediate, the thermally-stabilised modifying agent of lubricating oil, food
The aspects such as additive.1,6- hexanediol has two end position hydroxyls, and this structure can preferably participate in polyreaction, while 1,6-
The carbochain of hexanediol is longer, can effectively improve the mechanical strength of polymer.In terms of dyestuff and polyester, 1,6- oneself two
Alcohol improves the color and luster and absorbability of product, and with good light stability.1,6-HD is also widely used in
In the production of polyurethane, can effectively improve the hydrolytic resistance and mechanical strength of product, with 1,6- hexanediol for raw material production
Polyurethane its performance be much better than other kinds of polyurethane.In terms of the production of adhesive, with hexanediol as raw material production
Terephthalate has faster crystallization rate and more preferable viscosity, and excellent flexibility and adhesion are shown under cryogenic
Property.Therefore, hexanediol has been described as the new foundation stone of organic synthesiss.Chinese polyurethane, coiled material, the development band of paint industry
Increasing rapidly for domestic hexanediol consumption is moved, because 1, the 6- hexanediol imports dependency degree of domestic market is high and import volume is with every
Year 10% speed increase, thus exploitation possess independent intellectual property right 1,6- hexanediol production technologies it is very urgent.At present compared with
It is, for raw material, to carry out esterification with methanol and generate adipic acid diformazan with 1,6- adipic acids for ripe 1,6- hexanediol manufacture methods
Ester, then hydrogenated obtain 1,6- hexanediol.
US6407294B1 discloses a kind of method that prepared by adipate ester and 6 hydroxycaproic acid ester through hydrogenation into 1,6- hexanediol, urges
Agent contains copper, manganese and aluminum as basis, or using copper in Ruan.At 190 DEG C, 4.5MPa, hydrogen/ester mol ratio 280：
1, air speed 0.1 hour-1, feed stock conversion 100%, selectivity of product 98%, the preferable experimental result of the method acquirement, but
It is that the required hydrogen/ester mol ratio of reaction is of a relatively high.
CN102380389B discloses a kind of catalyst of hexanedioic acid dialkyl ester Hydrogenation for 1,6- hexanediol, the catalyst
In percentage composition by weight component：Cu 5-30%；Ni 2-10%；B 5-20%；Metallic addition M 0-5%；Porous is carried
Body surplus.The catalyst of preparation is reduced using sodium borohydride/potassium borohydride, is applied to 1,6- hexanedioic acid dialkyl esters
Hydrogenation in the reaction of hexanediol, reaction system desirable pressure higher (＞ 10MPa).
CN101531568 B disclose a kind of preparation method of dimethyl adipate hydrogenation catalyst：By mesopore silicon oxide carrier
And the aqueous solution containing mantoquita, stirring, microwave is evaporated, microwave drying and roasting, obtains final product hydrogenation catalyst.The inventive method
Middle employing microwave treatment catalyst, in commercial Application can not possibly large area use.Additionally, catalyst is for adipic acid two
In methyl ester hydrogenation reaction, feed stock conversion 90% or so, the selectivity ＜ 90% of product.
CN101113128 A disclose a kind of method of dimethyl adipate Hydrogenation for 1,6- hexanediol, wherein, catalyst
By weight percentage it is copper oxide 25～60%, Zinc Oxide 25～60%, aluminium oxide 10～30%, catalyst is used for adipic acid two
Methyl ester hydrogenation reaction prepares 1,6- hexanediol, feed stock conversion ＞ 99%, selectivity of product ＞ 96%.The patent is to catalyst
Details are not described further.
In sum, the Cu catalyst that prepared by prior art is applied to hexanedioic acid dialkyl ester Hydrogenation for 1,6- hexanediol mistakes
, there is the weak points such as hydrogen/ester mol ratio height, reaction pressure height, preparation method limitation, catalyst stability in Cheng Zhong.
The content of the invention
One of the technical problem to be solved is exist to be difficult to prepare the ester selectivity of good stability and add in prior art
The technical problem of hydrogen catalyst, there is provided a kind of new hexanedioic acid dialkyl ester Hydrogenation for 1,6- hexanediol catalyst, this is urged
Agent has the advantages that good stability, good conversion ratio and selectivity, catalyst are easy to molding.Skill solved by the invention
The two of art problem are to provide a kind of with purposes that is solving the corresponding catalyst of one of technical problem.
To solve one of above-mentioned technical problem, the technical solution used in the present invention is as follows：A kind of catalysis for preparing 1,6-HD
Agent, including following components in terms of parts by weight：
A) 20～50 parts of metallic coppers or its oxide；
B) 30～60 parts are selected from metallic zinc or its oxide；
C) 1～20 part of at least one element in transition metal or its oxide；
D) 1～20 part of alumina support.
In above-mentioned technical proposal, the specific surface area of alumina precursor is 100～500 meters2/ gram, preferably 200～450 meters2/
Gram, more preferably 300～450 meters2/ gram；Total pore volume is 0.3～2.0 ml/g, preferably 0.5～1.5 ml/g, more excellent
Elect 0.8～1.2 ml/g as；The pore volume that 20 nanometers of bore dia ＜ accounts for the 40～80% of total pore volume, and preferably 50～80%, more
Preferably 60～80%；The pore volume that 20～90 nanometers of bore dia accounts for the 10～40% of total pore volume, and preferably 20～40%, more preferably
For 25～35%；The pore volume that 90 nanometers of bore dia ＞ accounts for the 0～16% of total pore volume, and preferably 1～7%, more preferably 1～5%.
In above-mentioned technical proposal, in terms of parts by weight, the consumption of metallic copper or its oxide is preferably 25～45 parts, more preferably
For 30～45 parts；The consumption of metallic zinc or its oxide is preferably 35～55 parts, more preferably 40～55 parts；Selected from transition gold
The consumption of at least one element or its oxide in category is preferably 2～15 parts, more preferably 2～10 parts；Alumina support
Consumption is preferably 2～15 parts, more preferably 5～15 parts.
In above-mentioned technical proposal, selected from the element of transition metal at least one of manganese, zirconium, lanthanum, titanium or cerium are preferably selected from；
Element selected from transition metal is more preferably selected from least one of manganese, zirconium or cerium；Copper size of microcrystal in catalyst is 1～30
Nanometer, preferably 10～20 nanometers.
To solve the two of above-mentioned technical problem, the technical solution used in the present invention is as follows：The method that one kind prepares 1,6- hexanediol,
It is 100～250 in hydrogen/ester mol ratio with hexanedioic acid dialkyl ester and hydrogen as raw material, weight space velocity is 0.1～1.5 hour-1,
Reaction temperature is 150～250 DEG C, and reaction pressure is raw material and above-mentioned catalyst haptoreaction under the conditions of 1.0～10.0MPa,
The hexanedioic acid dialkyl ester in raw material is set to be hydroconverted into 1,6-HD.
In above-mentioned technical proposal, hydrogen ester mol ratio is preferably 150～200, and weight space velocity is preferably 0.1～0.6 hour-1, reaction
Temperature is preferably 180～240 DEG C, and reaction pressure is preferably 4.0～6.0MPa.
The preparation method of catalyst of the present invention is：A () is by mantoquita, zinc salt and builder salts wiring solution-forming I；(b) active component
Required deposited salt wiring solution-forming II；C () is placed in alumina support presoma in bottom water, in 50～90 DEG C of conditions, solution
I mixes with solution II, controls the pH of terminal 6.0～8.0, aging 3～6 hours, filters, scrubbed, dry, air
300～600 DEG C of roastings in atmosphere, compression molding obtains final product finished catalyst.Finished catalyst only need to lead to hydrogen also in the reactor
It is former to use.
The catalyst of the present invention is applied to the selection of hexanedioic acid dialkyl ester and is hydrogenated with, preferably to 1,6- dimethyl adipates or
The hydrogenation of 1,6- diethylene adipates.
The present invention catalyst be used for hexanedioic acid dialkyl ester Hydrogenation for 1,6- hexanediol during, copper, Cu oxide and
Its mixture is main active component, and the high dispersive of active component is the key factor of reactivity and catalyst stability.And
The catalyst of carrier is done using aluminium oxide, the more acidity of carrier surface has considerable influence, easily produces to the selectivity of product
The etherificate of thing, dehydration and it is dehydrated etherificate.Using the inventive method prepare alumina precursor by regulation and control gelling temperature, into
Glue pH value, so as to obtain the alumina precursor of high-specific surface area, high pore volume.It is standby for 1,6- di adipate Hydrogenations
1,6- hexanediol reaction itself, is primarily present four class side reactions：(1) there is raw material side reaction in dimethyl adipate, generate ring penta
Alcohol, methylcyclopentanol, cyclopentyl-ethanol；(2) the dehydration etherificate of product 1,6-HD generates hexamethylene ether；(3) product 1,6-
The excessive hydrogenation of hexanediol generates hexanol；(4) there is terminal hydroxy group dehydration generation 5- hexenols and 5- in product 1,6-HD
Hexene methyl ether；Wherein, (2), (3), (4) it is to be caused by the excess acid of carrier surface.In order to solve this problem, this
Bright adopted alumina support has larger specific surface area and abundant mesoporous, both ensure that the high score of active component
Dissipate, in turn ensure that the good thermal stability of Large ratio surface active carrier.The catalyst of the present invention is for 1,6- adipic acid diformazans
There is high feed stock conversion and high 1,6-HD selectivity during ester selective hydrogenation and catalyst activity keeps good.Adopt
The catalyst prepared with the present invention, is 200 DEG C in reaction temperature with dimethyl adipate and hydrogen as raw material, reaction pressure
For 5.0MPa, hydrogen/ester mol ratio is 170:1, air speed is 0.2 hour-1Under conditions of, dimethyl adipate conversion ratio ＞ 99%,
1,6- hexanediol liquid phase selective ＞ 97%, catalyst continuously runs 1000 hours, achieves preferable technique effect.
In concept used in the present invention, during 1,6- hexanedioic acid dialkyl ester Hydrogenation reacts for 1,6- hexanediol, 1,6- adipic acid
Dialkyl ester conversion ratio and 1,6-HD liquid phase selective computing formula are as follows：
Below by embodiment, the invention will be further elaborated, but these embodiments are not anyway to the present invention's
Scope is construed as limiting.
Specific embodiment
【Embodiment 1】
73.6 grams of nine water aluminum nitrate is weighed, the solution that concentration is 0.6M is configured to, is stirred, in being transferred to there-necked flask,
It is heated to 65 DEG C.The aluminum nitrate solution is neutralized with 25% ammonia, the pH value for controlling terminal is 8.6, and gel aging 4 is obtained
Hour, sucking filtration, washing is standby after 90 DEG C of dryings.
60.4 grams of nitrate trihydrate copper, 220.4 grams of zinc nitrate hexahydrate, 41.1 grams of 50% manganese nitrate solution are weighed, concentration is configured to
For the solution of 0.6M, as solution I；129.1 grams of sodium carbonate is weighed, the solution that concentration is 1.0M is configured to, it is as molten
Liquid II.The alumina precursor of preparation is placed in the liquid of bottom, 75 DEG C are heated to, solution I and the cocurrent Deca of solution II, control
Endpoint pH is 7.0 or so, and gained slurry is aging 3 hours, and Jing is filtered, and washing, 90 DEG C of dryings, 500 DEG C of roastings 4 are little
When, compression molding obtains catalyst C1, and catalyst composition transitivity data are shown in Table 1.
【Embodiment 2】
132.4 grams of nine water aluminum nitrate is weighed, the solution that concentration is 0.6M is configured to, is stirred, be transferred to there-necked flask
In, it is heated to 65 DEG C.The aluminum nitrate solution is neutralized with 25% ammonia, the pH value for controlling terminal is 8.6, and gel is obtained
Aging 4 hours, sucking filtration, washing was standby after 90 DEG C of dryings.
60.4 grams of nitrate trihydrate copper, 220.4 grams of zinc nitrate hexahydrate, 8.2 grams of 50% manganese nitrate solution are weighed, concentration is configured to
For the solution of 0.6M, as solution I；118.4 grams of sodium carbonate is weighed, the solution that concentration is 1.0M is configured to, it is as molten
Liquid II.The alumina precursor of preparation is placed in the liquid of bottom, 75 DEG C are heated to, solution I and the cocurrent Deca of solution II, control
Endpoint pH is 7.0 or so, and gained slurry is aging 3 hours, and Jing is filtered, and washing, 90 DEG C of dryings, 500 DEG C of roastings 4 are little
When, compression molding obtains catalyst C2, and catalyst composition transitivity data are shown in Table 1.
【Embodiment 3】
110.3 grams of nine water aluminum nitrate is weighed, the solution that concentration is 0.6M is configured to, is stirred, be transferred to there-necked flask
In, it is heated to 65 DEG C.The aluminum nitrate solution is neutralized with 25% ammonia, the pH value for controlling terminal is 8.6, and gel is obtained
Aging 4 hours, sucking filtration, washing was standby after 90 DEG C of dryings.
60.4 grams of nitrate trihydrate copper, 220.4 grams of zinc nitrate hexahydrate, 20.6 grams of 50% manganese nitrate solution are weighed, concentration is configured to
For the solution of 0.6M, as solution I；122.4 grams of sodium carbonate is weighed, the solution that concentration is 1.0M is configured to, it is as molten
Liquid II.The alumina precursor of preparation is placed in the liquid of bottom, 75 DEG C are heated to, solution I and the cocurrent Deca of solution II, control
Endpoint pH is 7.0 or so, and gained slurry is aging 3 hours, and Jing is filtered, and washing, 90 DEG C of dryings, 500 DEG C of roastings 4 are little
When, compression molding obtains catalyst C3, and catalyst composition transitivity data are shown in Table 1.
【Embodiment 4】
141.2 grams of nine water aluminum nitrate is weighed, the solution that concentration is 0.6M is configured to, is stirred, be transferred to there-necked flask
In, it is heated to 65 DEG C.The aluminum nitrate solution is neutralized with 25% ammonia, the pH value for controlling terminal is 8.6, and gel is obtained
Aging 4 hours, sucking filtration, washing was standby after 90 DEG C of dryings.
60.4 grams of nitrate trihydrate copper, 220.4 grams of zinc nitrate hexahydrate, 3.3 grams of 50% manganese nitrate solution are weighed, concentration is configured to
For the solution of 0.6M, as solution I；116.8 grams of sodium carbonate is weighed, the solution that concentration is 1.0M is configured to, it is as molten
Liquid II.The alumina precursor of preparation is placed in the liquid of bottom, 75 DEG C are heated to, solution I and the cocurrent Deca of solution II, control
Endpoint pH is 7.0 or so, and gained slurry is aging 3 hours, and Jing is filtered, and washing, 90 DEG C of dryings, 500 DEG C of roastings 4 are little
When, compression molding obtains catalyst C4, and catalyst composition transitivity data are shown in Table 1.
【Embodiment 5】
73.6 grams of nine water aluminum nitrate is weighed, the solution that concentration is 0.6M is configured to, is stirred, in being transferred to there-necked flask,
It is heated to 65 DEG C.The aluminum nitrate solution is neutralized with 25% ammonia, the pH value for controlling terminal is 8.0, and gel aging 4 is obtained
Hour, sucking filtration, washing is standby after 90 DEG C of dryings.
60.4 grams of nitrate trihydrate copper, 220.4 grams of zinc nitrate hexahydrate, 34.9 grams of five water zirconium nitrate are weighed, being configured to concentration is
The solution of 0.4M, as solution I；134.7 grams of sodium carbonate is weighed, the solution that concentration is 1.0M, as solution is configured to
Ⅱ.The alumina precursor of preparation is placed in the liquid of bottom, 75 DEG C are heated to, solution I and the cocurrent Deca of solution II, control is eventually
Point pH value is 7.0 or so, and gained slurry is aging 3 hours, and Jing is filtered, washing, 90 DEG C of dryings, 500 DEG C of roastings 4 hours,
Compression molding obtains catalyst C5, and catalyst composition transitivity data are shown in Table 1.
【Embodiment 6】
132.4 grams of nine water aluminum nitrate is weighed, the solution that concentration is 0.6M is configured to, is stirred, be transferred to there-necked flask
In, it is heated to 65 DEG C.The aluminum nitrate solution is neutralized with 25% ammonia, the pH value for controlling terminal is 8.0, and gel is obtained
Aging 4 hours, sucking filtration, washing was standby after 90 DEG C of dryings.
60.4 grams of nitrate trihydrate copper, 220.4 grams of zinc nitrate hexahydrate, 7.0 grams of five water zirconium nitrate are weighed, concentration is configured to for 0.4M
Solution, as solution I；119.5 grams of sodium carbonate is weighed, the solution that concentration is 1.0M, as solution II is configured to.
The alumina precursor of preparation is placed in the liquid of bottom, 75 DEG C are heated to, solution I and the cocurrent Deca of solution II control terminal
PH value is 7.0 or so, and gained slurry is aging 3 hours, and Jing is filtered, washing, 90 DEG C of dryings, 500 DEG C of roastings 4 hours,
Compression molding obtains catalyst C6, and catalyst composition transitivity data are shown in Table 1.
【Embodiment 7】
110.3 grams of nine water aluminum nitrate is weighed, the solution that concentration is 0.6M is configured to, is stirred, be transferred to there-necked flask
In, it is heated to 65 DEG C.The aluminum nitrate solution is neutralized with 25% ammonia, the pH value for controlling terminal is 8.0, and gel is obtained
Aging 4 hours, sucking filtration, washing was standby after 90 DEG C of dryings.
60.4 grams of nitrate trihydrate copper, 220.4 grams of zinc nitrate hexahydrate, 17.5 grams of five water zirconium nitrate are weighed, being configured to concentration is
The solution of 0.4M, as solution I；125.2 grams of sodium carbonate is weighed, the solution that concentration is 1.0M, as solution is configured to
Ⅱ.The alumina precursor of preparation is placed in the liquid of bottom, 75 DEG C are heated to, solution I and the cocurrent Deca of solution II, control is eventually
Point pH value is 7.0 or so, and gained slurry is aging 3 hours, and Jing is filtered, washing, 90 DEG C of dryings, 500 DEG C of roastings 4 hours,
Compression molding obtains catalyst C7, and catalyst composition transitivity data are shown in Table 1.
【Embodiment 8】
141.2 grams of nine water aluminum nitrate is weighed, the solution that concentration is 0.6M is configured to, is stirred, be transferred to there-necked flask
In, it is heated to 65 DEG C.The aluminum nitrate solution is neutralized with 25% ammonia, the pH value for controlling terminal is 8.0, and gel is obtained
Aging 4 hours, sucking filtration, washing was standby after 90 DEG C of dryings.
60.4 grams of nitrate trihydrate copper, 220.4 grams of zinc nitrate hexahydrate, 2.8 grams of five water zirconium nitrate are weighed, concentration is configured to for 0.4M
Solution, as solution I；117.2 grams of sodium carbonate is weighed, the solution that concentration is 1.0M, as solution II is configured to.
The alumina precursor of preparation is placed in the liquid of bottom, 75 DEG C are heated to, solution I and the cocurrent Deca of solution II control terminal
PH value is 7.0 or so, and gained slurry is aging 3 hours, and Jing is filtered, washing, 90 DEG C of dryings, 500 DEG C of roastings 4 hours,
Compression molding obtains catalyst C8, and catalyst composition transitivity data are shown in Table 1.
【Embodiment 9】
73.6 grams of nine water aluminum nitrate is weighed, the solution that concentration is 0.6M is configured to, is stirred, in being transferred to there-necked flask,
It is heated to 65 DEG C.The aluminum nitrate solution is neutralized with 25% ammonia, the pH value for controlling terminal is 8.6, and gel aging 4 is obtained
Hour, sucking filtration, washing is standby after 90 DEG C of dryings.
Weigh 60.4 grams of nitrate trihydrate copper, 220.4 grams of zinc nitrate hexahydrate, 20.6 grams of 50% manganese nitrate solution, five water zirconium nitrates
17.4 grams, it is configured to the solution that concentration is 0.4M, as solution I；131.9 grams of sodium carbonate is weighed, being configured to concentration is
The solution of 1.0M, as solution II.The alumina precursor of preparation is placed in the liquid of bottom, 75 DEG C are heated to, solution I with
The cocurrent Deca of solution II, control endpoint pH is 7.0 or so, and gained slurry is aging 3 hours, and Jing is filtered, washing, 90 DEG C
It is dried, 500 DEG C of roastings 4 hours, compression molding obtains catalyst C9, catalyst composition transitivity data are shown in Table 1.
【Embodiment 10】
58.8 grams of nine water aluminum nitrate, 8.2 grams of 50% manganese nitrate solution are weighed, the solution that concentration is 0.6M, stirring is configured to
Uniformly, it is transferred in there-necked flask, is heated to 50 DEG C.The aluminum nitrate solution is neutralized with 25% ammonia, terminal is controlled
PH value is 7.5, and prepared gel is aging 4 hours, sucking filtration, and washing is standby after 90 DEG C of dryings.
120.8 grams of nitrate trihydrate copper, 183.6 grams of zinc nitrate hexahydrate are weighed, the solution that concentration is 0.6M is configured to, it is as molten
Liquid I；65.4 grams of natrium carbonicum calcinatum, 40 grams of sodium hydroxide are weighed, the solution that concentration is 1.0M, as solution is configured to
Ⅱ.The alumina precursor of preparation is placed in the liquid of bottom, 75 DEG C are heated to, solution I and the cocurrent Deca of solution II, control is eventually
Point pH value is 7.0 or so, and gained slurry is aging 4 hours, and Jing is filtered, washing, 90 DEG C of dryings, 500 DEG C of roastings 4 hours,
Compression molding obtains catalyst C10, and catalyst composition transitivity data are shown in Table 1.
【Embodiment 11】
58.8 grams of nine water aluminum nitrate, 8.2 grams of 50% manganese nitrate solution are weighed, the solution that concentration is 0.6M, stirring is configured to
Uniformly, it is transferred in there-necked flask, is heated to 70 DEG C.The aluminum nitrate solution is neutralized with 25% ammonia, terminal is controlled
PH value is 8.0, and prepared gel is aging 4 hours, sucking filtration, and washing is standby after 90 DEG C of dryings.
120.8 grams of nitrate trihydrate copper, 183.6 grams of zinc nitrate hexahydrate are weighed, the solution that concentration is 0.6M is configured to, it is as molten
Liquid I；65.4 grams of natrium carbonicum calcinatum, 40 grams of sodium hydroxide are weighed, the solution that concentration is 1.0M, as solution is configured to
Ⅱ.The alumina precursor of preparation is placed in the liquid of bottom, 75 DEG C are heated to, solution I and the cocurrent Deca of solution II, control is eventually
Point pH value is 7.0 or so, and gained slurry is aging 4 hours, and Jing is filtered, washing, 90 DEG C of dryings, 500 DEG C of roastings 4 hours,
Compression molding obtains catalyst C11, and catalyst composition transitivity data are shown in Table 1.
【Embodiment 12】
58.8 grams of nine water aluminum nitrate, 8.2 grams of 50% manganese nitrate solution are weighed, the solution that concentration is 0.6M, stirring is configured to
Uniformly, it is transferred in there-necked flask, is heated to 65 DEG C.The aluminum nitrate solution is neutralized with 25% ammonia, terminal is controlled
PH value is 8.7, and prepared gel is aging 4 hours, sucking filtration, and washing is standby after 90 DEG C of dryings.
120.8 grams of nitrate trihydrate copper, 183.6 grams of zinc nitrate hexahydrate are weighed, the solution that concentration is 0.6M is configured to, it is as molten
Liquid I；65.4 grams of natrium carbonicum calcinatum, 40 grams of sodium hydroxide are weighed, the solution that concentration is 1.0M, as solution is configured to
Ⅱ.The alumina precursor of preparation is placed in the liquid of bottom, 75 DEG C are heated to, solution I and the cocurrent Deca of solution II, control is eventually
Point pH value is 7.0 or so, and gained slurry is aging 4 hours, and Jing is filtered, washing, 90 DEG C of dryings, 500 DEG C of roastings 4 hours,
Compression molding obtains catalyst C12, and catalyst composition transitivity data are shown in Table 1.
【Embodiment 13】
36.8 grams of nine water aluminum nitrate is weighed, the solution that concentration is 0.6M is configured to, is stirred, in being transferred to there-necked flask,
It is heated to 70 DEG C.The aluminum nitrate solution is neutralized with the sodium carbonate liquor that concentration is 0.6M, the pH value for controlling terminal is 7,
It is standby after prepared gel is aging 3 hours.
120.8 grams of nitrate trihydrate copper, 183.6 grams of zinc nitrate hexahydrate, 2.9 grams of Lanthanum (III) nitrate, 10.1 grams of six water cerous nitrate are weighed,
It is configured to the solution that concentration is 0.4M, as solution I；135.8 grams of sodium carbonate is weighed, concentration is configured to for the molten of 0.6M
Liquid, as solution II.The alumina precursor of preparation is placed in 70 DEG C of oil baths, solution I and the cocurrent Deca of solution II, control
Endpoint pH processed is 7.0 or so, and gained slurry is aging 4 hours, and Jing is filtered, washing, 90 DEG C of dryings, 450 DEG C of roastings 4
Hour, compression molding obtains catalyst C13, and catalyst composition transitivity data are shown in Table 1.
【Embodiment 14】
73.5 grams of nine water aluminum nitrate is weighed, the solution that concentration is 0.6M is configured to, titanium dioxide powder (1200 mesh number) 10 is added
Gram, stir, in being transferred to there-necked flask, it is heated to 75 DEG C.The nitre is neutralized with the sodium carbonate liquor that concentration is 0.6M
The mixed liquor of sour aluminum and titanium dioxide powder, the pH value for controlling terminal is 6.5, standby after prepared gel is aging 3 hours.
75.5 grams of nitrate trihydrate copper, 146.9 grams of zinc nitrate hexahydrate, 52.3 grams of five water zirconium nitrate are weighed, being configured to concentration is
The solution of 0.2M, as solution I；92.6 grams of sodium hydroxide is weighed, the solution that concentration is 0.4M, as solution is configured to
Ⅱ.The aluminium oxide and TiO 2 precursor of preparation are placed in 75 DEG C of oil baths, solution I and the cocurrent Deca of solution II, control
Endpoint pH is 7.0 or so, and gained slurry is aging 3 hours, and Jing is filtered, and washing, 90 DEG C of dryings, 550 DEG C of roastings 4 are little
When, compression molding obtains catalyst C14, and catalyst composition transitivity data are shown in Table 1.
【Embodiment 15】
110.3 grams of nine water aluminum nitrate is weighed, the solution that concentration is 0.6M is configured to, is stirred, be transferred to there-necked flask
In, it is heated to 75 DEG C.The aluminum nitrate solution is neutralized with the ammonia that concentration is 25%, the pH value for controlling terminal is 7, is obtained
It is standby after gel is aging 4 hours.
Weigh 105.7 grams of nitrate trihydrate copper, 165.3 grams of zinc nitrate hexahydrate, 12.3 grams of 50% manganese nitrate solution, the acid of six liquid glauber salt
5.0 grams of cerium, is configured to the solution that concentration is 0.5M, as solution I；122.2 grams of sodium carbonate is weighed, being configured to concentration is
The solution of 0.8M, as solution II.The alumina precursor of preparation is placed in 75 DEG C of oil baths, solution I is with solution II simultaneously
Drip adds, and control endpoint pH is 7.0 or so, and gained slurry is aging 4 hours, and Jing is filtered, washing, 90 DEG C of dryings,
500 DEG C of roastings 4 hours, compression molding obtains catalyst C15, and catalyst composition transitivity data are shown in Table 1.
【Comparative example 1】
The method provided according to patent CN1565729A prepares comparative example catalyst, and composition is calculated as 60 parts with parts by weight
CuO-20 part ZnO-10 part Al2O3- 10 parts of BaO.
Table 1
【Embodiment 16】
This example demonstrates that the gained catalyst of embodiment 1～15 should in dimethyl adipate or diethylene adipate select hydrogenation
With.
The each 30mL of the gained catalyst of the embodiment of the present invention 1～15 is taken, using pure hydrogen, at 300 DEG C 10h is reduced.With oneself
Adipate and pure hydrogen are raw material, change process conditions and are tested, and are analyzed using on-line chromatograph, 100 hours
Reaction result is shown in Table 2.
【Comparative example 2】
The gained catalyst 30ml of comparative example 1 is taken, is reduced 10 hours under 300 DEG C of pure hydrogen.With hexanedioic acid dialkyl ester and pure
Hydrogen is tested for raw material, is analyzed using on-line chromatograph, and reaction result is shown in Table 2.
Table 2
【Embodiment 17】
This example demonstrates that the gained catalyst C3 of embodiment 3 tests of 1000 hours in dimethyl adipate selects hydrogenation are tied
Really.
The gained catalyst C330mL of the embodiment of the present invention 3 is taken, using pure hydrogen, at 300 DEG C 10h is reduced.In reaction
Temperature is 200 DEG C, and reaction pressure is 5.0MPa, and hydrogen/ester mol ratio is 175:1, air speed is 0.2 hour-1Under conditions of,
Gained sample is analyzed using on-line chromatograph, and reaction result is shown in Table 3.
【Comparative example 3】
The gained catalyst CD130ml of comparative example 1 is taken, is reduced 10 hours under 300 DEG C of pure hydrogen.Take embodiment 17 identical
Raw material, same reaction conditions are tested, and reaction result is shown in Table 3.
Table 3
Claims (10)
1. one kind 1,6- hexanedioic acid dialkyl esters Hydrogenation is included with the following group for the catalyst of 1,6- hexanediol in terms of parts by weight
Point：
A) 20～50 parts of metallic coppers or its oxide；
B) 30～60 parts are selected from metallic zinc or its oxide；
C) 1～20 part of at least one element in transition metal or its oxide；
D) 1～20 part of alumina support.
2. 1,6- hexanedioic acid dialkyl esters Hydrogenation according to claim 1 for 1,6- hexanediol catalyst, its feature
The specific surface area for being alumina precursor is 100～500 meters2/ gram, total pore volume is 0.3～2.0 ml/g, bore dia ＜ 20
The pore volume of nanometer accounts for the 40～80% of total pore volume, and the pore volume that 20～90 nanometers of bore dia accounts for the 10～40% of total pore volume, bore dia ＞
90 nanometers of pore volume accounts for the 0～16% of total pore volume.
3. 1,6- hexanedioic acid dialkyl esters Hydrogenation according to claim 2 for 1,6- hexanediol catalyst, its feature
The specific surface area for being alumina precursor is 200～450 meters2/ gram, total pore volume is 0.5～1.5 ml/g, bore dia ＜ 20
The pore volume of nanometer accounts for the 50～80% of total pore volume, and the pore volume that 20～90 nanometers of bore dia accounts for the 20～40% of total pore volume, bore dia ＞
90 nanometers of pore volume accounts for the 1～7% of total pore volume.
4. 1,6- hexanedioic acid dialkyl esters Hydrogenation according to claim 3 for 1,6- hexanediol catalyst, its feature
The specific surface area for being alumina precursor is 300～450 meters2/ gram, total pore volume is 0.8～1.2 ml/g, bore dia ＜ 20
The pore volume of nanometer accounts for the 60～80% of total pore volume, and the pore volume that 20～90 nanometers of bore dia accounts for the 25～35% of total pore volume, bore dia ＞
90 nanometers of pore volume accounts for the 1～5% of total pore volume.
5. 1,6- hexanedioic acid dialkyl esters Hydrogenation according to claim 1 for 1,6- hexanediol catalyst, its feature
It is that in terms of parts by weight, the consumption of metallic copper or its oxide is 25～45 parts, the consumption of metallic zinc or its oxide is
35～55 parts, the consumption of at least one element or its oxide in transition metal is 2～15 parts, alumina support
Consumption is 2～15 parts.
6. 1,6- hexanedioic acid dialkyl esters Hydrogenation according to claim 5 for 1,6- hexanediol catalyst, its feature
It is that in terms of parts by weight, the consumption of metallic copper or its oxide is 30～45 parts, the consumption of metallic zinc or its oxide is
40～55 parts, the consumption of at least one element or its oxide in transition metal is 2～10 parts, alumina support
Consumption is 5～15 parts.
7. 1,6- hexanedioic acid dialkyl esters Hydrogenation according to claim 1 for 1,6- hexanediol catalyst, its feature
It is that the element for being selected from transition metal is selected from least one of manganese, zirconium, lanthanum, titanium or cerium.
8. 1,6- hexanedioic acid dialkyl esters Hydrogenation according to claim 7 for 1,6- hexanediol catalyst, its feature
It is that the element for being selected from transition metal is selected from least one of manganese, zirconium or cerium.
9. the method that one kind prepares 1,6- hexanediol, with 1,6- hexanedioic acid dialkyl esters and hydrogen for raw material, in hydrogen/ester mole
Than for 100～250, weight space velocity is 0.1～1.5 hour-1, reaction temperature is 150～250 DEG C, and reaction pressure is 1.0～10.0MPa
Under the conditions of, raw material and catalyst haptoreaction described in any one of claim 1～8 make 1, the 6- adipic acid dioxanes in raw material
Base ester is hydroconverted into 1,6-HD.
10. the method for preparing 1,6- hexanediol according to claim 9, it is characterised in that hydrogen/ester mol ratio is 150～200,
Weight space velocity is 0.1～0.6 hour-1, reaction temperature is 180～240 DEG C, and reaction pressure is 4.0～6.0MPa.
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