CN108607562A - Catalyst and preparation method and application for hexanedioic acid dialkyl ester hexylene glycol - Google Patents
Catalyst and preparation method and application for hexanedioic acid dialkyl ester hexylene glycol Download PDFInfo
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- CN108607562A CN108607562A CN201810412642.0A CN201810412642A CN108607562A CN 108607562 A CN108607562 A CN 108607562A CN 201810412642 A CN201810412642 A CN 201810412642A CN 108607562 A CN108607562 A CN 108607562A
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- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
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- C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
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Abstract
The present invention relates to a kind of Supported Cu catalyst, the catalyst contains Cu elements and M, and M refers to Ni, La, Mo, Mn, Fe, Co, Zn, one or more in Sn elements；The Cu elements are loaded on carrier with M, and the carrier is one or both of titanium dioxide and ceria.The catalyst is applied to by 1,6 hexanedioic acid dialkyl ester Hydrogenations for the reaction process of 1,6 hexylene glycols.The invention also includes the preparation methods of the catalyst.The catalyst hexanedioic acid dialkyl ester Hydrogenation is 150 250 DEG C of reaction temperature for the catalytic condition of hexylene glycol, and 2.0 5.0MPa of pressure, 1,6 hexanedioic acid dialkyl ester air speed is 0.2 1.0kg/kg.h, hydrogen ester molar ratio 100 200.Under the reaction conditions, 1, the conversion ratio 95~99% of 6 hexanedioic acid dialkyl esters；Selectivity is more than 97.0%, and impurity is less, reduces the difficulty isolated and purified.
Description
Technical field
The present invention relates to catalyst field, more particularly to it is a kind of be used for 1,6- hexanedioic acid dialkyl esters Hydrogenation 1,6- oneself
The preparation method and application of the catalyst of glycol and the catalyst.
Background technology
1,6- hexylene glycol, English name 1,6-hexanediol (HDO), molecular formula C6H14O2, 42 DEG C of fusing point, boiling point 250
DEG C, it is a kind of fine chemical material, unique properties have in UV coating, polyester, polyurethane, plasticizer, pesticide and medicine
It and is more and more widely used.There are two terminal hydroxy group, this structures can preferably participate in polymerisation for 1,6- hexylene glycol, together
When 1, the carbochain of 6- hexylene glycols is longer, can effectively improve the mechanical strength of polymer.In terms of fuel and polyester, 1,6-
Hexylene glycol improves the color and luster and adsorption capacity of product, and has good photostability.1,6-HD is also extensive
Applied in polyurethane field, it can effectively improve the hydrolytic resistance and mechanical strength of product.Therefore, 1,6- hexylene glycols quilt
It is described as the new foundation stone of organic synthesis.
The demand in China pair 1,6- hexylene glycols is increasing rapidly, wherein there is larger proportion to depend on import.Currently, state
There are German BASF, Lang Sheng, Ube etc., the only a small number of producer's energy in China in main 1,6- hexylene glycols production company on border
Enough a small amount of production, and process for producing is also in growth stage, in order to make up China in the sky for preparing 1,6- hexylene glycol techniques
It lacks, therefore, it is necessary to develop a kind of more efficient technique and catalyst for preparing 1,6- hexylene glycols.
Currently, 1,6- hexylene glycol mainly adds hydrogen to be made by 1,6- hexanedioic acid dialkyl esters.BASF AG is herein
Apply for that several such patents, major programme are that the by-product mixing of cyclohexanone/cyclohexanol is generated using cyclohexane oxidation in field
Carboxylic acid, wherein mixture of carboxylic acids mainly contain adipic acid, 6 hydroxycaproic acid, and Isosorbide-5-Nitrae-cyclohexanediol etc. mainly comprises the following steps mixing carboxylic
Esterification, purification, then 1,6- hexylene glycols are prepared in catalytic hydrogenation.Shandong Yuanli Science and Technology Co., Ltd.'s application
CN106748644A discloses a kind of method of adipic acid diethyl methyl esters gas phase hydrogenation production 1,6- hexylene glycols, is carried using a kind of carbon
Golden platinum nano catalyst needs catalyst being put into vibromill after preparing catalyst, before use and grinds activation, complex procedures
Cause cost quite high.The CN106607044A of Sinopec Group's application discloses a kind of adipic acid dialkyl group
Ester through hydrogenation prepares the catalyst and method of 1,6 hexylene glycols, and the catalyst is using aluminium oxide as carrier, carried metal copper or its oxidation
Object, metallic zinc or its oxide and transition metal element or its oxide.When using the catalyst, reaction pressure is about
10MPa is fluctuated between the selectivity 93.1~98% of conversion, and catalytic performance performance is unstable.Penta positive engineering technology of Shanghai is limited
The CN102380389A of company's application discloses one kind 1,6- hexanedioic acid dialkyl esters Hydrogenation 1, and the catalyst of 6- hexylene glycols should
Catalyst includes 5~30% bronze medals, nickel 2~10%, boron 5~20%, metallic addition M 0~5% and porous carrier surplus, more
Hole carrier is molecular sieve, activated carbon, gama-alumina and silica.Catalyst 1,6- hexanedioic acid dialkyl esters add hydrogen
When, reaction pressure is up to 14-20MPa, and conversion ratio 82.6%~98%, selectivity 85.5~99.6%, whole selectivity is not
Height, severe reaction conditions, product impurity content are more, purification difficult.Chinese patent application CN201080015253.6 discloses one kind
By esterified carboxy acid's mixture and the method that hydrogenates preparing ethylene glycol, the catalyst group which uses becomes CuO:ZnO:Al2O3
Mass ratio 70:25:5, reaction pressure 22MPa, increase equipment investment cost and operating cost higher to equipment requirement.
CN101679157A is the manufacturing method that the emerging Co., Ltd. of Ube applies for a kind of pentanediol or hexylene glycol, multiple using copper zinc
Conjunction catalyst hydrogenates in batch reactor obtains alcohol, 275 DEG C of reaction condition, reaction pressure 25MPa.Catalyst in this method
Use condition it is very harsh, fixed equipment investment and operational administrative cost can be increased, and Cu-series catalyst is easy at such high temperatures
It is sintered, activity reduces.
It can be seen that there are many deficiencies for the catalyst that uses of the prior art.
Invention content
For these reasons, the object of the present invention is to provide one kind having stably catalyzed performance under low-pressure low-temperature, makes oneself
The reduction reaction process of adipate Hydrogenation hexylene glycol has high-speed, highly selective and high conversion catalyst
And preparation method.
In order to solve the above problem of the prior art, the main technical schemes that the present invention uses include：
A kind of Supported Cu catalyst, the catalyst contain Cu elements and M, and M refers to Ni, La, Mo, Mn, Fe, Co,
It is one or more in Zn, Sn element；The Cu elements are loaded on carrier with M, and the carrier is titanium dioxide, two
One or both of cerium oxide.
Preferably, the Cu is present in the form of copper simple substance or Cu oxide in catalyst；The M with metal simple-substance or
Metal oxide form is present in catalyst.
Preferably, the molar ratio of the Cu and M is 1:(0~2).
Preferably, the mass fraction of carrier is 10~50% in the catalyst, and the Cu and M are in the form of an oxide
It is present in catalyst, wherein Cu oxides account for catalyst quality 20~70%, and M oxide accounts for catalyst quality 0~40%.
It should be noted that range above value does not include end value 0.
A kind of preparation method of catalyst for hexanedioic acid dialkyl ester Hydrogenation hexylene glycol, the method are：Xiang Tong
When can generate in the reaction system of the sediment of Cu and the sediment of M and put into powder carrier, the powder carrier is in institute
It states reaction system and is dispersed into suspended particulate；The powder carrier is selected from one or both of titanium dioxide, ceria；
The sediment of Cu and the sediment of M that the reaction system generates are attached on the carrier suspended particulate and form sediment,
The sediment is detached, roasting under sediment aerobic environment is obtained into support type Cu-M base catalyst；The wherein described M be Ni, La,
It is one or more in Mo, Mn, Fe, Co, Zn, Sn element.
Preferably, described method includes following steps：
S1：The preparation of metal salt solution：Soluble copper salt, soluble M salt are weighed, metal salt solution is configured to；
S2：Precipitation reaction：The powder carrier is added into the metal salt solution；It is in metal salt solution temperature
At 30~100 DEG C, alkaline solution is added dropwise thereto to pH=6~9, while being stirred continuously the hydroxide of the Cu and M that make generation
Absorption on the carrier, makes the carrier suspended particulate become larger and reforms sediment, sediment separate out obtains complex catalyst precursor
Body；
When metal salt solution temperature is 30~100 DEG C, it may make that reaction speed is very fast, the reaction of metal salt and alkali is more thorough
Bottom.
S3：Step S2 is obtained catalyst precursor to roast 1 at 300~700 DEG C~obtain support type Cu-M bases for 24 hours
Catalyst.
Preferably, the alkaline solution that step S2 is used is ammonium hydroxide, urea, ammonium carbonate, ammonium hydrogen carbonate, sodium hydroxide, carbonic acid
One or more mixing in sodium, sodium bicarbonate, potassium hydroxide, potassium carbonate, saleratus.
It is highly preferred that the alkaline solution that step S2 is used is ammonium hydroxide, urea, ammonium carbonate, ammonium hydrogen carbonate, sodium carbonate, carbonic acid
One or more mixing in hydrogen sodium, potassium carbonate, saleratus.Weakly alkaline solution can make the precipitation reaction speed phase of step S2
To slowly and at the uniform velocity, avoiding the hydroxide undue agglomeration of Cu and M on carrier, precipitate particles are excessive, and Cu and M are uniformly dispersed
Degree is poor, or even is sintered in roasting process.
Preferably, the soluble Cu salt in step S1 be in the nitrate of Cu, chlorate or acetate any one or
A variety of mixing；Any one or more mixing in nitrate, chlorate or acetate that the soluble M salt is M.
The invention also includes schemes：The support type Cu-M base catalyst is used to be added by 1,6- hexanedioic acid dialkyl esters
Hydrogen is prepared in the reaction process of 1,6- hexylene glycols, is activated the support type Cu-M base catalyst reductions at metal using preceding
The Cu-M base catalyst of state.
Preferably, it is control in reaction process of the raw material Hydrogenation for 1,6- hexylene glycols with 1,6- hexanedioic acid dialkyl esters
Condition is：Use 150-250 DEG C of the nitrogen and hydrogen mixture of hydrogen volume concentration 0.1-10%, reaction temperature, pressure 2.0-
The mass space velocity of 5.0MPa, 1,6- hexanedioic acid dialkyl ester are 0.2-1.0 kg/kg.h, hydrogen ester molar ratio 100-200.It is anti-at this
Under the conditions of answering, the conversion ratio of 1,6- hexanedioic acid dialkyl ester is more than 95%, and selectivity is more than 97.0%, and impurity is considerably less, therefore
The difficulty isolated and purified can be reduced.Alkyl in the 1,6- hexanedioic acid dialkyl esters is primarily referred to as methyl, ethyl, positive third
Base, isopropyl, normal-butyl, cyclohexyl etc. are one such or several.
The beneficial effects of the invention are as follows：
(1) compared with prior art, carrier is added in preparation method of the present invention in reactant aqueous solution system, and stirring makes
Carrier is dispersed into suspended particulate in aqueous solution, and sediment constantly absorption that copper ion and M ions are generated with alkaline solution and
It flocculates onto the suspended particulate substance, is precipitated out below solution, then detached, roasting obtains.Reaction process is in the solution
It carrying out, carrier has completely equivalent adsorption machine meeting to Cu sediments and M sediments, on the one hand Cu is made to be uniformly dispersed by M,
On the other hand the load capacity of Cu and M is also very uniform on each carrier granular, therefore can increase the homogeneity of catalyst material,
Stable catalytic performance is provided.
(2) present invention using Cu as major catalyst, can meet 1,6- hexanedioic acid dialkyl ester hydrogenating reductions prepare 1,6- oneself two
The realization of alcohol.It is co-catalyst to select metal M, one or more in M Ni, La, Mo, Mn, Fe, Co, Zn, Sn.Co-catalysis
Agent metal M can form alloy form with Cu, be conducive to the activity for improving Cu while M plays solid peptizaiton to Cu, prevent
Cu crystal or atom aggregation are agglomerating, improve the dispersion degree of Cu particles, increase the contact area of Cu and raw material, make preparation
Catalyst can play stronger catalytic activity.
(3) carrier is selected from one or both of titanium dioxide, ceria and is formed admittedly under roasting with Cu and metal M
Solution.Due to TiO2、CeO2There is oxygen vacancies in surface, and form one layer of very thin TiO under an atmosphere of hydrogen2-x、CeO2-xKnot
There is the solid solution that structure enables Cu and M to enter among hole, therefore formed stronger Metal-Support mutually to act synergistically,
The crystallite dimension for reducing Cu-M, improves the dispersion degree of metal, and the catalyst of preparation is made to have stronger catalytic activity.
(4) since stronger Metal-Support mutually acts synergistically, reduce particle and particle during catalyst use
Between the possibility reunited, improve the heat-resistant stability of catalyst, make the catalyst of preparation that there is longer service life.
(5) catalyst of the invention is using titanium dioxide and/or ceria as carrier, and titanium dioxide and ceria are all
It is amphoteric oxide, while there is the characteristic of lower weak acid and weak base.It is acid than common CuZnAl catalysis in this reaction
Aluminium oxide in agent is weaker, reduces alcohol and reacts the side reaction cracked in acid site at ether and organic matter, makes preparation
Catalyst have higher selectivity.
(6) catalyst of the invention is using titanium dioxide and/or ceria as carrier, based on the oxide of copper or copper
Catalyst, using metal M or its oxide as the load composite catalyst of co-catalyst, preparation process is simple, repeatable
By force, excellent catalytic effect, prepared catalyst are applied to have stronger practical significance in industrial production.
Specific implementation mode
In order to preferably explain the present invention, in order to understand, by specific implementation mode, the present invention is described in detail.
A kind of system of copper-based catalysts the invention discloses 1,6- hexanedioic acid dialkyl esters Hydrogenation for 1,6-HD
Preparation Method and its application, the practical catalyst includes at least three components：Including catalyst activity component Cu, co-catalyst M and
Carrier.Wherein co-catalyst M can be used for improving the performance of major catalyst Cu, including but not limited to ionic valence condition, acid-base property,
Surface texture, grain size etc., to make the activity, selectivity, stability of major catalyst Cu be improved.
Catalyst activity component Cu, co-catalyst M and three component of carrier synergistic effect make the performance of catalyst obtain obviously
Improvement.Major catalyst active component Cu is present in catalyst with the oxide form of copper or copper.Co-catalyst M with Ni,
One of La, Mo, Mn, Fe, Co, Zn or S or the form of several metal simple-substances or its oxide are present in catalyst.
The mass fraction of the oxide of Cu is between 20-70 in catalyst, and the mass fraction of the oxide of M is between 0-40, carrier
Mass fraction between 10-50.The molar ratio of copper and M element can be 1：Any number in (0-2).(aforementioned not
Containing endpoint value 0)
The preparation method of copper-based catalysts of the 1,6- hexanedioic acid dialkyl esters Hydrogenation of the present invention for 1,6-HD
For：Powder carrier is put into the reaction system that can generate the sediment of Cu and the sediment of M simultaneously, it is described powdered
Carrier is dispersed into suspended particulate in the reaction system；The one kind of the powder carrier in titanium dioxide, ceria
Or two kinds；The sediment of Cu and the sediment of M that the reaction system generates, which are attached to be formed on the carrier suspended particulate, to sink
Starch detaches the sediment, and roasting under sediment aerobic environment is obtained support type Cu-M base catalyst；The wherein described M is
It is one or more in Ni, La, Mo, Mn, Fe, Co, Zn, Sn element.
Preferably, described method includes following steps：
S1：The preparation of metal salt solution：Soluble copper salt, soluble M salt are weighed, metal salt solution is configured to；
S2：Precipitation reaction：The powder carrier is added into the metal salt solution；In metal salt solution temperature 30
At~100 DEG C, thereto be added dropwise alkaline solution to pH=6~9, while be stirred continuously the Cu and M that make generation hydroxide or
Carbonate adsorbs on the carrier, so that the carrier suspended particulate is become larger and reforms sediment, sediment separate out must be catalyzed
Agent presoma；
S3：Step S2 is obtained catalyst precursor to roast 1 at 300~700 DEG C~obtain support type Cu-M bases for 24 hours
Catalyst.
1,6- hexanedioic acid dialkyl esters Hydrogenation of the present invention is preferred for 1,6- adipic acids for 1,6-HD catalyst
Dialkyl ester Hydrogenation is not excluded for producing the reaction of other products for other organic acids and/ester through hydrogenation for 1,6- hexylene glycols
In.When the catalyst is used for reaction of 1, the 6- hexanedioic acid dialkyl esters Hydrogenation for 1,6- hexylene glycols, reaction temperature 150-
250 DEG C, pressure 2.0-5.0MPa, the mass space velocity of 1,6- hexanedioic acid dialkyl ester is 0.2-1.0kg/kg.h, and hydrogen ester ratio is
Under the reaction condition of 100-200,95~99.9%, for high selectivity up to 97.0~98.5%, impurity is less, and reduction isolates and purifies
Difficulty.
Preparation example
Embodiment 1
30g copper chlorides (III) hydrate is weighed, 5g cabaltous nitrate hexahydrates are made into 1000 mL metal salts in volumetric flask
Aqueous solution.The ammonium hydroxide of 25-28% is added in aqueous solution in the environment of 40 DEG C to metal salt until endpoint pH is 7.5；To
20g titanium dioxide is added in solution and continuing stirring makes precipitation adsorption on carrier titanium dioxide in 4 hours, obtains quasi- catalyst；
Then it by quasi- catalyst filtration to filter out impurity therein, and is washed with water, it is 12 hours dry in the environment of 100 DEG C, it obtains
Catalyst；Catalyst is taken out in Muffle kiln roasting, is warming up to 400 DEG C from room temperature with the rate of 10 DEG C/min, and holding 4 is small
When roast, be then slowly dropped to room temperature and obtain Cu-M base catalyst, referred to as Cat-1.
Embodiment 2
120g copper acetates (II) dimer, 20g acetic acid molybdenums are weighed, 20g nickel nitrates are made into 1L metal salts in volumetric flask
Aqueous solution is placed in large beaker.The sodium hydroxide water of 1.0mol/L is added in aqueous solution in the environment of 80 DEG C to metal salt
Solution is until endpoint pH is 6.5；50g cerias are added into solution and continuing stirring makes precipitation adsorption in carrier in 4 hours
On ceria, quasi- catalyst is obtained；Then by quasi- catalyst filtration, filter out impurity therein, and be washed with water, in 120 DEG C
In the environment of obtain catalyst within dry 8 hours；Catalyst is taken out in Muffle kiln roasting, from room temperature with the rate of 5 DEG C/min
550 DEG C are warming up to, and 8h is kept to roast, then slow cooling to room temperature, obtains Cu-M catalyst, referred to as Cat-2.
Embodiment 3
100g copper chlorides (III) hydrate is weighed, 20g tetra- is hydrated manganese acetate and is matched in the volumetric flask of 1000mL
Metal salt solution is made.The aqueous sodium carbonate that 1.0mol/L is added in aqueous solution in the environment of 60 DEG C to metal salt is straight
PH value is 8.0 to terminal；25g titanium dioxide and 25g cerias are added into solution, and continuing stirring makes precipitation inhale in 6 hours
It is attached on carrier, obtains quasi- catalyst；Then by quasi- catalyst filtration, impurity therein is filtered out, and be washed with water, in 120 DEG C
Obtain catalyst within dry 10 hours under dry environment；Catalyst is taken out in Muffle kiln roasting, from room temperature with the speed of 5 DEG C/min
Rate is warming up to 650 DEG C, and 10h is kept to roast；Then slow cooling obtains Cu-M catalyst, referred to as Cat-3 to room temperature.
Embodiment 4
50g copper acetates (II) dimer, 10g cobalt acetates are weighed, 10g zinc acetates are matched in the volumetric flask of 1000mL
At metal salt solution.The aqueous solution of urea of 1.0mol/L is added in aqueous solution in the environment of 60 DEG C to metal salt until end
Point pH value is 7.0；50g titanium dioxide is added into solution and continuing stirring makes precipitation adsorption in carrier titanium dioxide in 6 hours
On, obtain quasi- catalyst；Then quasi- catalyst filtration to filter out impurity therein, and is washed with water, in the environment of 120 DEG C
It is 10 hours dry, obtain catalyst.Catalyst is taken out in Muffle kiln roasting, is warming up to from room temperature with the rate of 5 DEG C/min
350 DEG C, and 10h is kept to roast.Then slow cooling obtains Cu-M catalyst, referred to as Cat-4 to room temperature.
Embodiment 5
50g copper acetates (II) dimer is weighed, 10.5g nickel nitrates, 10g zinc acetates are in the volumetric flask of 1000mL, by it
It is made into metal salt solution.The aqueous sodium carbonate that 1.0mol/L is added in aqueous solution in the environment of 60 DEG C to metal salt is straight
PH value is 7.0 to terminal；50g titanium dioxide is added into solution and continuing stirring makes precipitation adsorption in carrier titanium dioxide in 6 hours
On titanium, quasi- catalyst is obtained；Then quasi- catalyst filtration to filter out impurity therein, and is washed with water, in 120 DEG C of environment
Lower drying 10 hours, obtains catalyst.Catalyst is taken out in Muffle kiln roasting, is heated up from room temperature with the rate of 5 DEG C/min
To 350 DEG C, and 10h is kept to roast.Then slow cooling obtains Cu-M catalyst, referred to as Cat-5 to room temperature.
Embodiment 6
50g copper acetates (II) dimer is weighed, 24.5g lanthanum nitrates, 10g zinc acetates are in the volumetric flask of 1000mL, by it
It is made into metal salt solution.The wet chemical that 1.0mol/L is added in aqueous solution in the environment of 60 DEG C to metal salt is straight
PH value is 7.0 to terminal；50g titanium dioxide is added into solution and continuing stirring makes precipitation adsorption in carrier titanium dioxide in 6 hours
On titanium, quasi- catalyst is obtained；Then quasi- catalyst filtration to filter out impurity therein, and is washed with water, in 120 DEG C of environment
Lower drying 10 hours, obtains catalyst.Catalyst is taken out in Muffle kiln roasting, is heated up from room temperature with the rate of 5 DEG C/min
To 350 DEG C, and 10h is kept to roast.Then slow cooling obtains Cu-M catalyst, referred to as Cat-6 to room temperature.
Embodiment 7
120g copper acetates (II) dimer, 11.4g ferric nitrates are weighed, 20g nickel nitrates are made into 1L metal salts in volumetric flask
Aqueous solution, be placed in large beaker.The sodium hydroxide of 1.0mol/L is added in aqueous solution in the environment of 80 DEG C to metal salt
Aqueous solution is until endpoint pH is 6.5；30 g cerias and 20g titanium dioxide are added into solution, and continues stirring 4 hours
Make precipitation adsorption on carrier, obtains quasi- catalyst；Then by quasi- catalyst filtration, filter out impurity therein, and be washed with water
It washs, obtain catalyst within dry 8 hours in the environment of 120 DEG C；Catalyst is taken out in Muffle kiln roasting, from room temperature with 5 DEG C/
The rate of min is warming up to 550 DEG C, and 8h is kept to roast, then slow cooling to room temperature, obtains Cu-M catalyst, referred to as Cat-
7。
Embodiment 8
50g Gerhardites are weighed, 20g zinc nitrate hexahydrates are made into the water-soluble of 1000mL metal salts in volumetric flask
Liquid.The ammonium hydroxide of 25-28% is added in aqueous solution in the environment of 60 DEG C to metal salt until endpoint pH is 7.5；To solution
Middle addition 10g cerias and continuing stirring makes precipitation adsorption on carrier ceria in 4 hours, obtain quasi- catalyst；Then
By quasi- catalyst filtration to filter out impurity therein, and it is washed with water, it is 12 hours dry in the environment of 100 DEG C, it is catalyzed
Agent；Catalyst is taken out in Muffle kiln roasting, is warming up to 400 DEG C from room temperature with the rate of 10 DEG C/min, and keep roasting for 4 hours
It burns, is then slowly dropped to room temperature and obtains Cu-M base catalyst, referred to as Cat-8.
Comparative example 1
This comparative example is that the carrier ceria of embodiment 8 is replaced with carrier γ-on the basis of embodiment 8
Al2O3, thus compare when carrier is changed to γ-Al by ceria2O3When, the influence to the catalytic performance of final catalyst.Tool
Gymnastics is made as follows：
50g Gerhardites are weighed, 20g zinc nitrate hexahydrates are made into the water-soluble of 1000mL metal salts in volumetric flask
Liquid.The ammonium hydroxide of 25-28% is added in aqueous solution in the environment of 60 DEG C to metal salt until endpoint pH is 7.5；To solution
Middle addition 10g alundum (Al2O3)s (γ-Al2O3) and continuing stirring makes precipitation adsorption on carrier alundum in 4 hours, obtains
Quasi- catalyst；Then it by quasi- catalyst filtration to filter out impurity therein, and is washed with water, dry 12 in the environment of 100 DEG C
Hour, obtain catalyst；Catalyst is taken out in Muffle kiln roasting, 400 DEG C are warming up to from room temperature with the rate of 10 DEG C/min,
And keep roasting for 4 hours, it is then slowly dropped to room temperature and obtains Cu-M base catalyst, be labeled as Cat-1-D.
Comparative example 2
Catalyst is prepared according to the method that Chinese patent application CN105727962 patent specifications embodiment 1 is recorded, is obtained
To Cu-Zn-Al-Zr catalyst, it is labeled as Cat-2-D.
Catalytic performance test method
By the catalyst prepared by catalyst and comparative example 1-2 obtained in above-described embodiment 1-8, be respectively used to from
Dimethyl adipate Hydrogenation 1 in the reaction process of 6- hexylene glycols, and investigates the catalytic performance of above-mentioned catalyst.
The reduction and evaluation procedure of above-mentioned catalyst are in the tubular fixed-bed reaction of the laboratory scale of Φ 10*700mm
It is carried out on device.Catalyst, the constant temperature zone of reactor is fixed on quartz sand by the catalyst of 20-40 mesh after taking 10g to roast.Make
The nitrogen and hydrogen mixture for being 0.1-10% with volume ratio is restored.
1,6- dimethyl adipates are pumped by liquid feedstock, and are vaporized by preheater, then are mixed with hydrogen
After be sent into reactor, the mass space velocity of 1,6- dimethyl adipate is 0.2-1.0/ hour, and hydrogen ester molar ratio is 100-200.Instead
System condensation water cooling, is detached, liquid is collected in wet tank using gas-liquid separator after answering.In reaction process
In, condensed product liquid sample was taken out every 1 hour, was formed with its product of gas chromatographic analysis；It takes altogether preceding 100 small
When product liquid sample, and calculate by area normalization method the conversion ratio and 1 of 1,6- dimethyl adipates, 6- hexylene glycols
Selectivity, last averaged (two columns record average value on the right side of following table).Wherein the conversion ratio of dimethyl adipate and
The selectivity of 1,6-HD calculates according to the following formula：
The conversion ratio of dimethyl adipate=(the peak area percentage composition of 1-dimethyl adipate) × 100%.
The peak area percentage composition of selectivity=1,6-HD of 1,6-HD/(the peak face of 1-dimethyl adipate
The peak area percentage composition of product percentage composition-methanol) × 100%.
Reaction result see the table below：
From the above test result：
Catalyst prepared by embodiment 1-8, when being catalyzed reaction of the dimethyl adipate Hydrogenation for 1,6- hexylene glycols,
Reaction condition is in 180~230 DEG C, 3.0~5.0MPa of pressure of temperature, hydrogen ester molar ratio 120~200,0.3~0.8h of air speed-1
Under, the high conversion rate of 1,6- dimethyl adipate up to the high selectivity of 95.9~99.1%, 1,6- hexylene glycols up to 97.0% with
On, target product impurity is less, can effectively reduce the difficulty isolated and purified.
The catalyst Cat-1-D conversion ratios that wherein prepared by comparative example 1 are about 94.2%, selectivity about 94.5%；Comparison
Catalyst Conversion prepared by example Cat-2-D is about 95.3%, selectivity about 95.5%.It can be seen that prepared by the present invention
Catalyst participates in hydrogenation reaction, and reaction effect is more preferable compared with comparative example, main reason is that having used titanium dioxide and/or two
Cerium oxide is the Cu base catalyst of carrier, can obtain preferable catalytic effect.According to conjecture, it may be possible to the Cu- that comparative example 2 obtains
The catalyst of Zn-Al-Zr prepares the mixed liquor of soluble-salt with zirconium chloride soluble-salt and Cu salt, Zn salt, and it is heavy to be then added
Agent aluminium hydroxide in shallow lake forms precipitation, and gained catalyst is the common distribution body of four kinds of metals, causes major catalyst Cu by transition
Dilution, reduces its catalytic performance.
Conclusion：The reality that hexanedioic acid dialkyl ester Hydrogenation reacts for 1,6-HD can be completed using copper-based catalysts
It applies.High activity, highly selective and the long-life catalyst can be prepared for carrier using titanium dioxide and/or ceria, is urged
Change superior performance, preparation method is simple, is conducive to industrial applications.
Claims (10)
1. a kind of Supported Cu catalyst, which is characterized in that the catalyst contains Cu elements and M, and M refers to Ni, La, Mo, Mn,
It is one or more in Fe, Co, Zn, Sn element；The Cu elements are loaded on carrier with M, and the carrier is titanium dioxide
One or both of titanium and ceria.
2. a kind of Supported Cu catalyst according to claim 1, which is characterized in that the Cu is with copper simple substance or copper oxygen
Compound form is present in catalyst；The M is present in metal simple-substance or metal oxide form in catalyst.
3. a kind of Supported Cu catalyst according to claim 2, which is characterized in that the molar ratio of the Cu and M is
1:(0~2).
4. a kind of Supported Cu catalyst according to claim 3, which is characterized in that the matter of carrier in the catalyst
It is 10~50% to measure score, and the Cu and M are present in catalyst in the form of an oxide, and wherein Cu oxides account for catalyst matter
Amount 20~70%, M oxide accounts for catalyst quality 0~40%.
5. a kind of preparation method of catalyst for hexanedioic acid dialkyl ester Hydrogenation hexylene glycol, the method are：To simultaneously
It can generate and put into powder carrier in the reaction system of the sediment of Cu and the sediment of M, the powder carrier is described
Reaction system is dispersed into suspended particulate；The powder carrier is selected from one or both of titanium dioxide, ceria；It is described
The sediment of Cu and the sediment of M that reaction system generates are attached on the carrier suspended particulate and form sediment, and separation should
Roasting under sediment aerobic environment is obtained support type Cu-M base catalyst by sediment；The wherein described M be Ni, La, Mo, Mn,
It is one or more in Fe, Co, Zn, Sn element.
6. preparation method according to claim 5, which is characterized in that described method includes following steps：
S1：The preparation of metal salt solution：Soluble copper salt, soluble M salt are weighed, metal salt solution is configured to；
S2：Precipitation reaction：The powder carrier is added into the metal salt solution；In metal salt solution temperature 30~100
At DEG C, alkaline solution is added dropwise thereto to pH=6~9, while being stirred continuously makes the hydroxide of the Cu and M of generation be adsorbed on institute
It states on carrier, so that the carrier suspended particulate is become larger and reform sediment, sediment separate out obtains catalyst precursor；
S3：Step S2 is obtained catalyst precursor to roast 1 at 300~700 DEG C~obtain the catalysis of support type Cu-M bases for 24 hours
Agent.
7. preparation method according to claim 6, which is characterized in that the alkaline solution that step S2 is used be ammonium hydroxide, urea,
One kind or more in ammonium carbonate, ammonium hydrogen carbonate, sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide, potassium carbonate, saleratus
Kind mixing.
8. preparation method according to claim 6, which is characterized in that described method includes following steps：In step S1
Any one or more mixing in nitrate, chlorate or acetate that soluble Cu salt is Cu；The soluble M salt is M
Nitrate, any one or more mixing in chlorate or acetate.
9. the catalyst prepared by Supported Cu catalyst or claim 5-8 described in claim 1-4 by 1,6- oneself
Adipate Hydrogenation is for the application in the reaction process of 1,6-HD.
10. application according to claim 9, which is characterized in that standby for raw material Hydrogenation with 1,6- hexanedioic acid dialkyl esters
In the reaction process of 1,6- hexylene glycol, the alkyl is methyl, ethyl, n-propyl, isopropyl, normal-butyl or cyclohexyl；Reaction
When control condition be：Use 150-250 DEG C of the nitrogen and hydrogen mixture of hydrogen volume concentration 0.1-10%, reaction temperature, pressure 2.0-
5.0MPa, 1,6- hexanedioic acid dialkyl ester air speed are 0.2-1.0kg/kg.h, hydrogen ester molar ratio 100-200.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110215920A (en) * | 2019-07-03 | 2019-09-10 | 中溶科技股份有限公司 | Preparing isopropyl alcohol by acetone hydrogenation catalyst and its preparation method and application |
| CN111701591A (en) * | 2020-06-16 | 2020-09-25 | 北京石油化工学院 | Hydrogenation catalyst, preparation method thereof and method for preparing fatty alcohol by hydrogenation of fatty acid ester |
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