CN114163302B - Preparation method of 3-methyl-1, 5-pentanediol - Google Patents

Preparation method of 3-methyl-1, 5-pentanediol Download PDF

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CN114163302B
CN114163302B CN202111431591.4A CN202111431591A CN114163302B CN 114163302 B CN114163302 B CN 114163302B CN 202111431591 A CN202111431591 A CN 202111431591A CN 114163302 B CN114163302 B CN 114163302B
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methyl
pentanediol
hydrogenation
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CN114163302A (en
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王联防
刘英俊
庞计昌
张红涛
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Wanhua Chemical Group Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
    • C07C29/172—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds with the obtention of a fully saturated alcohol
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8993—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with chromium, molybdenum or tungsten
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

The invention discloses a preparation method of 3-methyl-1, 5-pentanediol. The unsaturated dihydric alcohol crude product is subjected to hydrogenation reaction under the action of a hydrogenation catalyst, wherein the unsaturated dihydric alcohol is one or more of 3-methylene-1, 5-pentanediol, trans-3-methyl-2-alkene-1, 5-pentanediol and cis-3-methyl-2-alkene-1, 5-pentanediol. The hydrogenation catalyst comprises 1 to 5wt% of ruthenium and 0.1 to 0.5 wt% of molybdenum as active metal elements, and the carrier comprises Lu 2 O 3 、Fe 2 O 3 And Sc (Sc) 2 O 3 . The process remarkably improves the utilization value of the waste liquid and can reduce the running cost of the device.

Description

Preparation method of 3-methyl-1, 5-pentanediol
Technical Field
The invention relates to the field of organic synthesis, in particular to a method for preparing 3-methyl-1, 5-pentanediol by taking an unsaturated dihydric alcohol crude product recovered from waste liquid as a raw material through catalytic hydrogenation reaction.
Background
3-methyl-1, 5-pentanediol (hereinafter abbreviated as MPD) is an isomer of 1, 6-hexanediol, and methyl branches in the structure impart various unique properties such as non-crystallinity and hydrophobicity, and thus is used for preparing polyester resins having special properties, alkyd resins for coating materials, etc., giving polyurethane excellent flexibility, high transparency and compatibility.
At present, the industrial main stream synthesis process of MPD takes 3-methyl-3-butene-1 alcohol as a raw material, and is prepared by a series of reactions such as hydroformylation, cyclization, hydrogenation and the like. The related art is disclosed in US4663468, CN101432255B by japan colali corporation. U.S. Pat. No. 3,182,62 discloses a direct hydroformylation process of 3-methyl-3-buten-1-ol, the reaction product comprising, in addition to 2-hydroxy-4-Methyltetrahydropyran (MHP), a number of by-products, such as isovaleraldehyde, bis (4-methyl-tetrahydropyran-2-methyl) ether (main by-product), with a reaction selectivity of only about 50%.
CN101432255B discloses a process for preparing 3-methyl-1, 5-pentanediol by hydrogenating 2-hydroxy-4-methyltetrahydropyran in the presence of a hydrogenation catalyst, and in order to effectively suppress the formation of by-products, it is inevitably necessary to add an alkaline compound to the reaction system, but nevertheless the formation of by-products is unavoidable up to 5%. However, since some by-products have a boiling point close to that of MPD, it is not practical to completely separate the MPD by a separation means reused in industry, and when polymerization reaction of polyester or polyurethane is carried out by using MPD having a high content of some by-products, end capping of polymerization end is likely to occur, which results in a series of problems such as a smaller molecular weight of the polymer. Therefore, it is important to increase the purity of MPD as much as possible.
In summary, the process of synthesizing and preparing 3-methyl-1, 5-pentanediol under the condition of the prior art scheme has more steps and relatively harsh conditions, and various side reactions, such as isomerization of double bonds, isomerization of enol to aldehyde, cyclization, condensation reaction and the like, are inevitably excited, so that a series of problems of low reaction yield, difficult post-treatment and the like are caused.
Disclosure of Invention
The invention provides a method for preparing 3-methyl-1, 5-pentanediol by catalytic hydrogenation reaction by taking an unsaturated diol crude product recovered from waste liquid as a raw material.
The waste liquid is derived from a synthesis process of 3-methyl-3-butene-1-ol, isobutene and formaldehyde are used as raw materials, a crude product is obtained at the top of a de-weight tower to obtain a target product, and heavy components in the tower bottom are directly used as the waste liquid for incineration treatment. However, the heavy component waste liquid contains unsaturated dihydric alcohol which can be recycled, namely 3-methyl-2-alkene-1, 5-pentanediol and isomers thereof, and the structural formula is as follows:
the invention directly obtains important saturated dihydric alcohol 3-methyl-1, 5-pentanediol by hydrogenating the unsaturated dihydric alcohol, avoids unnecessary byproducts, obviously improves the value of waste liquid and can reduce the running cost of the device.
In order to achieve the above object, the present invention adopts the following technical scheme:
a method for preparing 3-methyl-1, 5-pentanediol, comprising the following steps: the unsaturated dihydric alcohol crude product is subjected to hydrogenation reaction under the action of a hydrogenation catalyst, wherein the unsaturated dihydric alcohol is one or more of 3-methylene-1, 5-pentanediol, trans-3-methyl-2-alkene-1, 5-pentanediol and cis-3-methyl-2-alkene-1, 5-pentanediol.
The unsaturated dihydric alcohol crude product has the components of unsaturated dihydric alcohol with mass fraction not lower than 80%.
As another scheme, the unsaturated dihydric alcohol crude product contains 85-95 wt% of unsaturated dihydric alcohol and 0.1-5.0 wt% of 3-methyl-3-butene-1-ol,
the invention provides a hydrogenation catalyst comprising an active metal and a support. The hydrogenation catalyst comprises 1 to 5wt% of ruthenium and 0.1 to 0.5 wt% of molybdenum as active metal elements, and the carrier comprises Lu 2 O 3 、Fe 2 O 3 And Sc (Sc) 2 O 3 。
The preparation method of the hydrogenation catalyst comprises the following steps:
1) Lu (Lu) 2 O 3 、Fe 2 O 3 And Sc (Sc) 2 O 3 According to the amount of the substance 1: (10-50): (0.2-1) is added into a ball mill and ground for 1-5 h; then roasting for 5-20 hours at 1000-1500 ℃ in nitrogen atmosphere, and cooling to room temperature to obtain a carrier;
2) Dispersing a carrier in water, dropwise adding an active metal salt solution into the carrier, simultaneously dropwise adding an alkali solution into the carrier for coprecipitation, filtering, roasting the carrier for 1 to 20 hours at the temperature of between 500 and 800 ℃ in a nitrogen atmosphere, and cooling the carrier to the room temperature to obtain a supported catalyst precursor;
3) And (3) reducing the supported catalyst precursor in a hydrogen atmosphere to obtain the hydrogenation catalyst.
The active metal salt of the invention can be ruthenium chloride and molybdenum chloride.
The alkali liquor can be 1-10wt% sodium hydroxide aqueous solution, potassium hydroxide aqueous solution and the like.
In the step (3), the reduction temperature is 70-200 ℃, the reduction time is 2-25 h, preferably 100-150 ℃ and the reduction time is 5-10 h.
In the selection of hydrogenation catalysts, although the known hydrogenation catalysts such as Raney Ni, pd/C and the like can be used for realizing high-efficiency conversion, the service life of the catalyst is short, and the catalyst cannot be effectively used twice or more, which obviously increases the process cost of waste recycling. The main reason for this dilemma is that unsaturated diols recovered from waste streams contain numerous impurities, including 3-methyl-3-buten-1-ol which is not completely separated, and these substances contain unsaturated bonds or structures such as ether bonds (typical impurity molecules are shown in the following formula), and have better adsorption and combination with active components (such as atomic Ni, co, ru and the like) or carriers (such as active carbon and the like) of catalysts, occupy active sites, or further intermolecular polymerization reaction occurs after adsorption, pore channels are blocked or active sites are covered, and the normal adsorption hydrogenation of main reaction substrate molecules can be obviously inhibited, so that the main reaction is prevented.
Without being limited by any theory, the catalyst in the present invention, fe 2 O 3 As a main component of the carrier, lu was added 2 O 3 And Sc (Sc) 2 O 3 Compared with pure Fe, the composite carrier prepared by the method 2 O 3 The carrier has higher surface area, abundant surface defects and better electron transfer effect, when the ruthenium and molybdenum double-active components are dispersed on the surface of the composite carrier in an atomic state, the active components have quite high dispersity, the hydrogenation activity and selectivity of the active components are fully exerted, the strong adsorption effect on impurities containing unsaturated bonds or ether bonds and other structures is reduced, the active sites of the catalyst are prevented from losing activity quickly in the hydrogenation process, and the service life of the catalyst is prolonged.
In the present invention, the hydrogenation catalyst can be used as a catalyst for a fixed bed and a tank reactor.
In the hydrogenation reaction, the addition amount of the hydrogenation catalyst is 0.5-5% of the addition amount of the crude diol, and the reaction system can be selected without using other solvents, so that the working procedures such as post-treatment and the like are greatly simplified.
In the hydrogenation reaction, the reaction temperature is 60-150 ℃, preferably 80-100 ℃, the reaction pressure is 0.1-10 Mpa, preferably 1-5 Mpa, and the reaction time is 2-24 h, preferably 5-10 h.
In the hydrogenation reaction, the conversion rate of the reaction is not lower than 98%, and the selectivity of a target product is not lower than 99.5%.
Detailed Description
The following examples will further illustrate the method provided by the present invention, but the invention is not limited to the examples listed and should also include any other known modifications within the scope of the claims.
The analysis method comprises the following steps:
gas chromatograph: agilent7890, column wax (conversion, selectivity assay), sample inlet temperature: 300 ℃; split ratio 50:1, a step of; the carrier gas flow is 52.8ml/min; heating program: maintaining at 150deg.C for 10min, increasing to 260deg.C at 10deg.C/min, maintaining for 5min, and detecting temperature: 280 ℃.
ICP (inductively coupled plasma emission spectrometer): the device is used for metal element detection, focal length of 0.38m, echelle grating lines of 52.6 pieces/mm, a 21-degree prism, a charge injection type (CID) detector, a 512×512 detection unit, a wavelength range of 175 nm-1050 nm, a high-frequency generator, high-frequency power of 2.0KW, 3 turns of a working coil, frequency of 27.12MHz, a glass concentric atomizer, a rotational flow fog chamber and a built-in 4-channel peristaltic pump. The analysis conditions were as follows: high frequency power: 1.15KW, plasma gas flow: 15L/min, auxiliary air flow: 0.5L/min, peristaltic pump rotation speed: 100rpm, observed height: 15mm, atomizing air pressure: 0.22MPa, integration time: the long wave is larger than 275nm 15S, and the short wave is smaller than 275nm 25S.
The medicine is used:
crude unsaturated dihydric alcohol, and self-made in laboratory
98wt% ruthenium chloride, ara Ding Shiji Co;
99.6wt% molybdenum chloride, ara Ding Shiji Co., ltd;
99wt% sodium hydroxide, ara Ding Shiji Co., ltd;
Lu 2 O 3 99.9wt%, ala Ding Shiji Co., ltd;
Fe 2 O 3 99.5wt%, ala Ding Shiji Co., ltd;
Sc 2 O 3 99.9wt%, ala Ding Shiji Co., ltd;
activated carbon (coconut shells, water absorption 200%), jiangsu Zhuxi activated carbon Co., ltd.
Example 1
The preparation process of the composite carrier comprises the following steps:
a) Lu (Lu) 2 O 3 、Fe 2 O 3 And Sc (Sc) 2 O 3 According to the amount of the substance 1:10: feeding the materials to a ball mill according to the proportion of 0.2, and stopping grinding after 1 h;
b) Roasting the mixture in the step a) at 1200 ℃ in a nitrogen atmosphere for 15 hours, and cooling to room temperature after roasting to obtain a composite carrier;
the preparation process of the hydrogenation catalyst comprises the following steps:
a) 9.86g of composite carrier is introduced into water and fully stirred until the composite carrier is uniformly dispersed;
b) The active components ruthenium and molybdenum are added into a) simultaneously in the form of 0.21g of ruthenium chloride and 0.02g of molybdenum chloride, in order to precipitate the catalytic active components on the carrier, naOH saturated solution is slowly added, and when the PH of the mixed solution is stabilized at 9, alkali solution is stopped to be added dropwise;
c) Separating the coprecipitate from the water phase by filtering to obtain a filter cake;
d) Roasting at 500 ℃ in nitrogen atmosphere for 10 hours, and cooling to room temperature after roasting is finished to obtain a supported catalyst precursor;
e) The supported catalyst precursor is reduced at 100 ℃ in a hydrogen atmosphere for 5 hours, and cooled to room temperature after the reduction is finished to obtain the composite oxygenMetal ruthenium-molybdenum catalyst supported by the compound, namely 1% Ru-0.1% Mo/Lu 2 O 3 -Fe 2 O 3 -Sc 2 O 3 ；
Reaction performance evaluation:
2g of 1% Ru-0.1% Mo/Lu were successively added to a 500ml hydrogenation autoclave 2 O 3 -Fe 2 O 3 -Sc 2 O 3 200g of crude unsaturated diol (81 wt% of unsaturated diol, typical impurity content is as follows: 4.7wt% of 3-methyl-3-buten-1-ol, 1.50 wt% of impurity molecule, and 2.65 wt% of impurity molecule) was replaced 3 times with nitrogen and hydrogen, heating and stirring were started, and hydrogen was charged to 3MPa at 80℃and maintained for 8 hours until the reaction was completed. The reaction results were analyzed by GC and are shown in table 1.
Example 2
The preparation process of the composite carrier comprises the following steps:
a) Lu (Lu) 2 O 3 、Fe 2 O 3 And Sc (Sc) 2 O 3 According to the amount of the substance 1:20:0.4, feeding the materials to a ball mill, and stopping grinding after 2 hours;
b) Placing the mixture in the step a) in a nitrogen atmosphere for roasting at 1100 ℃ for 5 hours, and cooling to room temperature after roasting is finished to obtain a composite carrier;
the preparation process of the hydrogenation catalyst comprises the following steps:
a) 9.75g of composite carrier is introduced into water and fully stirred until the composite carrier is uniformly dispersed;
b) The active components ruthenium and molybdenum are added into a) simultaneously in the form of 0.42g of ruthenium chloride and 0.11g of molybdenum chloride, in order to precipitate the catalytic active components on the carrier, naOH saturated solution is slowly added, and when the PH of the mixed solution is stabilized at 9, alkali solution is stopped to be added dropwise;
c) Separating the coprecipitate from the water phase by filtering to obtain a filter cake;
d) Roasting at 570 ℃ in nitrogen atmosphere for 5h, and cooling to room temperature after roasting is finished to obtain a supported catalyst precursor;
e) The supported catalyst precursor is reduced at 110 ℃ in a hydrogen atmosphere for 6h, and cooled to room temperature after the reduction is finishedTo obtain the composite oxide supported metal ruthenium-molybdenum catalyst, namely 2 percent Ru-0.5 percent Mo/Lu 2 O 3 -Fe 2 O 3 -Sc 2 O 3 ；
Reaction performance evaluation:
5g of 2% Ru-0.5% Mo/Lu were successively added to a 500ml hydrogenation autoclave 2 O 3 -Fe 2 O 3 -Sc 2 O 3 200g of crude unsaturated diol (85% by weight of unsaturated diol, typical impurity content is as follows: 2.50% by weight of 3-methyl-3-buten-1-ol, 1.89% by weight of impurity molecule, 22.86% by weight of impurity molecule) was replaced 3 times with nitrogen and hydrogen each, heating and stirring were started, and hydrogen was charged to 2MPa at a temperature of 85℃and maintained for 5 hours until the reaction was completed. The reaction results were analyzed by GC and are shown in table 1.
Example 3
The preparation process of the composite carrier comprises the following steps:
a) Lu (Lu) 2 O 3 、Fe 2 O 3 And Sc (Sc) 2 O 3 According to the amount of the substance 1:30:1, feeding the materials to a ball mill in proportion, and stopping grinding after 3 hours;
b) Placing the mixture in the step a) in a nitrogen atmosphere for roasting at 1000 ℃ for 10 hours, and cooling to room temperature after roasting is finished to obtain a composite carrier;
the preparation process of the hydrogenation catalyst comprises the following steps:
a) 9.66g of composite carrier is introduced into water and fully stirred until the composite carrier is uniformly dispersed;
b) The active components ruthenium and molybdenum are added into a) simultaneously in the form of 0.63g of ruthenium chloride and 0.08g of molybdenum chloride, in order to precipitate the catalytic active components on the carrier, naOH saturated solution is slowly added, and when the PH of the mixed solution is stabilized at 9, alkali solution is stopped to be added dropwise;
c) Separating the coprecipitate from the water phase by filtering to obtain a filter cake;
d) Roasting at 650 ℃ in nitrogen atmosphere for 1h, and cooling to room temperature after roasting to obtain a supported catalyst precursor;
e) The supported catalyst precursor is reduced under the hydrogen atmosphere at 125 ℃ for 7h to reduce the junctionAfter the beam, cooling to room temperature to obtain the composite oxide supported metal ruthenium-molybdenum catalyst, namely 3 percent Ru-0.4 percent Mo/Lu 2 O 3 -Fe 2 O 3 -Sc 2 O 3 ；
Reaction performance evaluation:
1g of 3% Ru-0.4% Mo/Lu were successively added to a 500ml hydrogenation autoclave 2 O 3 -Fe 2 O 3 -Sc 2 O 3 200g of crude unsaturated diol (93 wt% of unsaturated diol, typical impurity content is as follows: 0.8wt% of 3-methyl-3-buten-1-ol, 1.30 wt% of impurity molecule, 2.00 wt% of impurity molecule) was replaced 3 times with nitrogen and hydrogen each, heating and stirring were started, and hydrogen was charged to 4MPa when the temperature was raised to 90℃and maintained for 6 hours until the reaction was completed. The reaction results were analyzed by GC and are shown in table 1.
In addition, the catalyst of this example was used as a catalyst, and the result of the use is shown in Table 2.
Example 4
The preparation process of the composite carrier comprises the following steps:
a) Lu (Lu) 2 O 3 、Fe 2 O 3 And Sc (Sc) 2 O 3 According to the amount of the substance 1:40: feeding the materials to a ball mill according to the proportion of 0.8, and stopping grinding after 4 hours;
b) Placing the mixture in the step a) in a nitrogen atmosphere at 1300 ℃ for roasting for 8 hours, and cooling to room temperature after roasting is finished to obtain a composite carrier;
the preparation process of the hydrogenation catalyst comprises the following steps:
a) 9.57g of composite carrier is introduced into water and fully stirred until the composite carrier is uniformly dispersed;
b) The active components ruthenium and molybdenum are added into a) simultaneously in the form of 0.84g of ruthenium chloride and 0.06g of molybdenum chloride, in order to precipitate the catalytic active components on the carrier, naOH saturated solution is slowly added, and when the PH of the mixed solution is stabilized at 9, alkali solution is stopped to be added dropwise;
c) Separating the coprecipitate from the water phase by filtering to obtain a filter cake;
d) Roasting at 730 ℃ in nitrogen atmosphere for 15h, and cooling to room temperature after roasting to obtain a supported catalyst precursor;
e) The supported catalyst precursor is reduced under the hydrogen atmosphere at 135 ℃ for 8 hours, and cooled to room temperature after the reduction is finished, thus obtaining the composite oxide supported metal ruthenium-molybdenum catalyst, namely 4 percent Ru-0.3 percent Mo/Lu 2 O 3 -Fe 2 O 3 -Sc 2 O 3 ；
Reaction performance evaluation:
7g of 4% Ru-0.3% Mo/Lu were added successively in a 500ml hydrogenation autoclave 2 O 3 -Fe 2 O 3 -Sc 2 O 3 200g of crude unsaturated diol (90 wt% of unsaturated diol, typical impurity content is as follows: 0.4wt% of 3-methyl-3-buten-1-ol, 1.50 wt% of impurity molecule, 2.23 wt% of impurity molecule) was replaced 3 times with nitrogen and hydrogen each, heating and stirring were started, and hydrogen was charged to 1MPa when the temperature was raised to 95℃and maintained for 7 hours until the reaction was completed. The reaction results were analyzed by GC and are shown in table 1.
Example 5
The preparation process of the composite carrier comprises the following steps:
a) Lu (Lu) 2 O 3 、Fe 2 O 3 And Sc (Sc) 2 O 3 According to the amount of the substance 1:50: feeding the materials to a ball mill according to the proportion of 0.6, and stopping grinding after 5 hours;
b) Placing the mixture in the step a) in a nitrogen atmosphere for roasting at 1500 ℃ for 20 hours, and cooling to room temperature after roasting is finished to obtain a composite carrier;
the preparation process of the hydrogenation catalyst comprises the following steps:
a) 9.48g of composite carrier is introduced into water and fully stirred until the composite carrier is uniformly dispersed;
b) The active components ruthenium and molybdenum are added into a) simultaneously in the form of 1.05g of ruthenium chloride and 0.04g of molybdenum chloride, in order to precipitate the catalytic active components on the carrier, naOH saturated solution is slowly added, and when the PH of the mixed solution is stabilized at 9, alkali solution is stopped to be added dropwise;
c) Separating the coprecipitate from the water phase by filtering to obtain a filter cake;
d) Roasting at 800 ℃ in nitrogen atmosphere for 20h, and cooling to room temperature after roasting to obtain a supported catalyst precursor;
e) The supported catalyst precursor is reduced at 150 ℃ in a hydrogen atmosphere for 10 hours, and cooled to room temperature after the reduction is finished, so as to obtain the composite oxide supported metal ruthenium-molybdenum catalyst, namely 5 percent Ru-0.2 percent Mo/Lu 2 O 3 -Fe 2 O 3 -Sc 2 O 3 ；
Reaction performance evaluation:
10g of 5% Ru-0.2% Mo/Lu were successively added to a 500ml hydrogenation autoclave 2 O 3 -Fe 2 O 3 -Sc 2 O 3 200g of crude unsaturated diol (88 wt% of unsaturated diol, typical impurity content is as follows: 0.6wt% of 3-methyl-3-buten-1-ol, 1.10 wt% of impurity molecule, 2.74 wt% of impurity molecule), 3 times of replacement with nitrogen and hydrogen are respectively carried out, heating and stirring are started, hydrogen is filled to 5MPa when the temperature is raised to 100 ℃, and the reaction is maintained for 10 hours until the end. The reaction results were analyzed by GC and are shown in table 1.
Example 6
The preparation process of the composite carrier comprises the following steps:
a) Lu (Lu) 2 O 3 、Fe 2 O 3 And Sc (Sc) 2 O 3 According to the amount of the substance 1:30:1, feeding the materials to a ball mill in proportion, and stopping grinding after 3 hours;
b) Placing the mixture in the step a) in a nitrogen atmosphere for roasting at 1000 ℃ for 10 hours, and cooling to room temperature after roasting is finished to obtain a composite carrier;
the preparation process of the hydrogenation catalyst comprises the following steps:
a) 9.66g of composite carrier is introduced into water and fully stirred until the composite carrier is uniformly dispersed;
b) The active components ruthenium and molybdenum are added into a) simultaneously in the form of 0.63g of ruthenium chloride and 0.08g of molybdenum chloride, in order to precipitate the catalytic active components on the carrier, naOH saturated solution is slowly added, and when the PH of the mixed solution is stabilized at 9, alkali solution is stopped to be added dropwise;
c) Separating the coprecipitate from the water phase by filtering to obtain a filter cake;
d) Roasting at 650 ℃ in nitrogen atmosphere for 1h, and cooling to room temperature after roasting to obtain a supported catalyst precursor;
e) The supported catalyst precursor is reduced under the hydrogen atmosphere at 125 ℃ for 7h, and cooled to room temperature after the reduction is finished, thus obtaining the composite oxide supported metal ruthenium-molybdenum catalyst, namely 3 percent Ru-0.4 percent Mo/Lu 2 O 3 -Fe 2 O 3 -Sc 2 O 3 ；
Reaction performance evaluation:
1g of 3% Ru-0.4% Mo/Lu were successively added to a 500ml hydrogenation autoclave 2 O 3 -Fe 2 O 3 -Sc 2 O 3 200g of crude unsaturated diol (92.1 wt% of unsaturated diol, typical impurity content is as follows: 1.9wt% of 3-methyl-3-buten-1-ol, 1.1wt% of impurity molecule, and 2.60 wt% of impurity molecule) was replaced 3 times with nitrogen and hydrogen each, heating and stirring were started, and hydrogen was charged to 4MPa when the temperature was raised to 90℃and maintained for 6 hours until the reaction was completed. The reaction results were analyzed by GC and are shown in table 1.
Comparative example 1
The preparation process of the composite carrier comprises the following steps:
a) Lu (Lu) 2 O 3 、Fe 2 O 3 And Sc (Sc) 2 O 3 According to the amount of the substance 1:30:1, feeding the materials to a ball mill in proportion, and stopping grinding after 3 hours;
b) Placing the mixture in the step a) in a nitrogen atmosphere for roasting at 1000 ℃ for 10 hours, and cooling to room temperature after roasting is finished to obtain a composite carrier;
the preparation process of the hydrogenation catalyst comprises the following steps:
a) 9.96g of composite carrier is introduced into water and fully stirred until the composite carrier is uniformly dispersed;
b) The active component molybdenum is added into a) at the same time in the form of 0.08g of molybdenum chloride metal salt, in order to precipitate the catalytic active component on the carrier, naOH saturated solution is slowly added, and when the PH of the mixed solution is stabilized at 9, alkali solution is stopped to be added dropwise;
c) Separating the coprecipitate from the water phase by filtering to obtain a filter cake;
d) Roasting at 650 ℃ in nitrogen atmosphere for 1h, and cooling to room temperature after roasting to obtain a supported catalyst precursor;
e) The supported catalyst precursor is reduced at 125 ℃ in a hydrogen atmosphere for 7h, and cooled to room temperature after the reduction is finished, thus obtaining the composite oxide supported metal ruthenium-molybdenum catalyst, namely 0.4 percent Mo/Lu 2 O 3 -Fe 2 O 3 -Sc 2 O 3 ；
Reaction performance evaluation:
1g of 0.4% Mo/Lu was added successively to a 500ml hydrogenation autoclave 2 O 3 -Fe 2 O 3 -Sc 2 O 3 200g of crude unsaturated diol (the specific composition is the same as in example 3), the crude unsaturated diol is replaced with nitrogen and hydrogen for 3 times, heating and stirring are started, hydrogen is filled to 4MPa when the temperature is raised to 90 ℃, and the reaction is maintained for 6 hours until the end. The reaction results were analyzed by GC and are shown in table 1.
Comparative example 2
The preparation process of the composite carrier comprises the following steps:
a) Lu (Lu) 2 O 3 、Fe 2 O 3 And Sc (Sc) 2 O 3 According to the amount of the substance 1:30:1, feeding the materials to a ball mill in proportion, and stopping grinding after 3 hours;
b) Placing the mixture in the step a) in a nitrogen atmosphere for roasting at 1000 ℃ for 10 hours, and cooling to room temperature after roasting is finished to obtain a composite carrier;
the preparation process of the hydrogenation catalyst comprises the following steps:
a) 9.70g of composite carrier is introduced into water and fully stirred until the composite carrier is uniformly dispersed;
b) The active component ruthenium is added into a) at the same time in the form of 0.63g of ruthenium chloride metal salt, in order to precipitate the catalytic active component on the carrier, naOH saturated solution is slowly added, and when the PH of the mixed solution is stabilized at 9, alkali solution is stopped to be added dropwise;
c) Separating the coprecipitate from the water phase by filtering to obtain a filter cake;
d) Roasting at 650 ℃ in nitrogen atmosphere for 1h, and cooling to room temperature after roasting to obtain a supported catalyst precursor;
e) The carried catalyst precursor is under the hydrogen atmosphere at 125 DEG CReducing for 7h, and cooling to room temperature after the reduction is finished to obtain the composite oxide supported metal ruthenium molybdenum catalyst, namely 3 percent Ru/Lu 2 O 3 -Fe 2 O 3 -Sc 2 O 3 ；
Reaction performance evaluation:
1g of 3% Ru/Lu were added successively to a 500ml hydrogenation autoclave 2 O 3 -Fe 2 O 3 -Sc 2 O 3 200g of crude unsaturated diol (the specific composition is the same as in example 3), the crude unsaturated diol is replaced with nitrogen and hydrogen for 3 times, heating and stirring are started, hydrogen is filled to 4MPa when the temperature is raised to 90 ℃, and the reaction is maintained for 6 hours until the end. The reaction results were analyzed by GC and are shown in table 1.
Comparative example 3
The preparation process of the composite carrier comprises the following steps:
a) Lu (Lu) 2 O 3 And Fe (Fe) 2 O 3 According to the amount of the substance 1:30, feeding the materials to a ball mill, grinding for 3 hours, and stopping;
b) Placing the mixture in the step a) in a nitrogen atmosphere for roasting at 1000 ℃ for 10 hours, and cooling to room temperature after roasting is finished to obtain a composite carrier;
the preparation process of the hydrogenation catalyst comprises the following steps:
a) 9.66g of composite carrier is introduced into water and fully stirred until the composite carrier is uniformly dispersed;
b) The active components ruthenium and molybdenum are added into a) simultaneously in the form of 0.63g of ruthenium chloride and 0.08g of molybdenum chloride, in order to precipitate the catalytic active components on the carrier, naOH saturated solution is slowly added, and when the PH of the mixed solution is stabilized at 9, alkali solution is stopped to be added dropwise;
c) Separating the coprecipitate from the water phase by filtering to obtain a filter cake;
d) Roasting at 650 ℃ in nitrogen atmosphere for 1h, and cooling to room temperature after roasting to obtain a supported catalyst precursor;
e) The supported catalyst precursor is reduced under the hydrogen atmosphere at 125 ℃ for 7h, and cooled to room temperature after the reduction is finished, thus obtaining the composite oxide supported metal ruthenium-molybdenum catalyst, namely 3 percent Ru-0.4 percent Mo/Lu 2 O 3 -Fe 2 O 3 ；
Reaction performance evaluation:
1g of 3% Ru-0.4% Mo/Lu were successively added to a 500ml hydrogenation autoclave 2 O 3 -Fe 2 O 3 200g of crude unsaturated diol (the specific composition is the same as in example 3), the crude unsaturated diol is replaced with nitrogen and hydrogen for 3 times, heating and stirring are started, hydrogen is filled to 4MPa when the temperature is raised to 90 ℃, and the reaction is maintained for 6 hours until the end. The reaction results were analyzed by GC and are shown in table 1.
Comparative example 4
The preparation process of the carrier comprises the following steps:
a) A certain amount of Lu 2 O 3 Feeding the materials to a ball mill, and stopping after grinding for 3 hours;
b) Roasting the mixture in the step a) at 1000 ℃ in a nitrogen atmosphere for 10 hours, and cooling to room temperature after roasting to obtain a carrier;
the preparation process of the hydrogenation catalyst comprises the following steps:
a) 9.66g of carrier is introduced into water and fully stirred until the carrier is uniformly dispersed;
b) The active components ruthenium and molybdenum are added into a) simultaneously in the form of 0.63g of ruthenium chloride and 0.08g of molybdenum chloride, in order to precipitate the catalytic active components on the carrier, naOH saturated solution is slowly added, and when the PH of the mixed solution is stabilized at 9, alkali solution is stopped to be added dropwise;
c) Separating the coprecipitate from the water phase by filtering to obtain a filter cake;
d) Roasting at 650 ℃ in nitrogen atmosphere for 1h, and cooling to room temperature after roasting to obtain a supported catalyst precursor;
e) The supported catalyst precursor is reduced under the hydrogen atmosphere at 125 ℃ for 7h, and cooled to room temperature after the reduction is finished, so as to obtain the oxide supported metal ruthenium-molybdenum catalyst, namely 3 percent Ru-0.4 percent Mo/Lu 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the Reaction performance evaluation:
1g of 3% Ru-0.4% Mo/Lu were successively added to a 500ml hydrogenation autoclave 2 O 3 200g of crude unsaturated diol (the specific composition is the same as in example 3), nitrogen is usedThe gas and the hydrogen are replaced for 3 times respectively, heating and stirring are started, the hydrogen is filled to 4MPa when the temperature is raised to 90 ℃, and the reaction is maintained for 6 hours until the end. The reaction results were analyzed by GC and are shown in table 1.
Comparative example 5
The preparation process of the carrier comprises the following steps:
a) To a certain amount of Fe 2 O 3 Feeding the materials to a ball mill, and stopping after grinding for 3 hours;
b) Roasting the mixture in the step a) at 1000 ℃ in a nitrogen atmosphere for 10 hours, and cooling to room temperature after roasting to obtain a carrier;
the preparation process of the hydrogenation catalyst comprises the following steps:
a) 9.66g of carrier is introduced into water and fully stirred until the carrier is uniformly dispersed;
b) The active components ruthenium and molybdenum are added into a) simultaneously in the form of 0.63g of ruthenium chloride and 0.08g of molybdenum chloride, in order to precipitate the catalytic active components on the carrier, naOH saturated solution is slowly added, and when the PH of the mixed solution is stabilized at 9, alkali solution is stopped to be added dropwise;
c) Separating the coprecipitate from the water phase by filtering to obtain a filter cake;
d) Roasting at 650 ℃ in nitrogen atmosphere for 1h, and cooling to room temperature after roasting to obtain a supported catalyst precursor;
e) The supported catalyst precursor is reduced under the hydrogen atmosphere at 125 ℃ for 7h, and cooled to room temperature after the reduction is finished, so as to obtain the oxide supported metal ruthenium-molybdenum catalyst, namely 3 percent Ru-0.4 percent Mo/Fe 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the Reaction performance evaluation:
1g of 3% Ru-0.4% Mo/Fe were successively added to a 500ml hydrogenation autoclave 2 O 3 200g of crude unsaturated diol (the specific composition is the same as in example 3), the crude unsaturated diol is replaced with nitrogen and hydrogen for 3 times, heating and stirring are started, hydrogen is filled to 4MPa when the temperature is raised to 90 ℃, and the reaction is maintained for 6 hours until the end. The reaction results were analyzed by GC and are shown in table 1.
Comparative example 6
The preparation process of the hydrogenation catalyst comprises the following steps:
a) 9.66g of active carbon carrier is introduced into water and fully stirred until the active carbon carrier is uniformly dispersed;
b) The active components ruthenium and molybdenum are added into a) simultaneously in the form of 0.63g of ruthenium chloride and 0.08g of molybdenum chloride, in order to precipitate the catalytic active components on the carrier, naOH saturated solution is slowly added, and when the PH of the mixed solution is stabilized at 9, alkali solution is stopped to be added dropwise;
c) Separating the coprecipitate from the water phase by filtering to obtain a filter cake;
d) Roasting at 650 ℃ in nitrogen atmosphere for 1h, and cooling to room temperature after roasting to obtain a supported catalyst precursor;
e) The supported catalyst precursor is reduced at 125 ℃ in a hydrogen atmosphere for 7h, and cooled to room temperature after the reduction is finished, so as to obtain the oxide supported metal ruthenium-molybdenum catalyst, namely 3 percent Ru-0.4 percent Mo/C; reaction performance evaluation:
1g of 3% Ru-0.4% Mo/C and 200g of crude unsaturated dihydric alcohol (the specific composition is the same as that of example 3) are sequentially added into a 500ml hydrogenation reaction pressure kettle, nitrogen and hydrogen are used for replacement for 3 times respectively, heating and stirring are started, hydrogen is filled to 4MPa when the temperature is raised to 90 ℃, and the reaction is maintained for 6 hours until the end. The reaction results were analyzed by GC and are shown in table 1.
Table 1 example comparative example results
Table 2 example 3 set of results
Batch for application Conversion% 3-methyl-1, 5-pentanediol selectivity%
1 99.20 99.77
2 99.70 99.54
3 98.30 99.81
4 99.10 99.88
5 99.50 99.56
10 98.80 99.89
15 98.90 99.77
20 99.20 99.82
25 99.60 99.54

Claims (8)

1. The preparation method of the 3-methyl-1, 5-pentanediol comprises the following steps of carrying out hydrogenation reaction on a crude unsaturated dihydric alcohol under the action of a hydrogenation catalyst, wherein the unsaturated dihydric alcohol is one or more of 3-methylene-1, 5-pentanediol, trans-3-methyl-2-ene-1, 5-pentanediol and cis-3-methyl-2-ene-1, 5-pentanediol;
the unsaturated dihydric alcohol crude product has the components of unsaturated dihydric alcohol content of 85-95 wt% and 3-methyl-3-butene-1-ol content of 0.1-5.0 wt%,the content of (C) is 1.0-6.0 wt%,>the content of (2) is 0.5-5.0wt%;
the hydrogenation catalyst comprises 1 to 5 weight percent of ruthenium and 0.1 to 0.5 weight percent of molybdenum as active metal elements, and further comprises a carrier, wherein the carrier comprises Lu 2 O 3 、Fe 2 O 3 And Sc (Sc) 2 O 3 。
2. The process according to claim 1, characterized in that the preparation process of the hydrogenation catalyst comprises the following steps:
1) Lu (Lu) 2 O 3 、Fe 2 O 3 And Sc (Sc) 2 O 3 According to the amount of the substance 1: (10-50): (0.2-1) is added into a ball mill and ground for 1-5 h; then roasting for 5-20 hours at 1000-1500 ℃ in nitrogen atmosphere, and cooling to room temperature to obtain a carrier;
2) Dispersing a carrier in water, dropwise adding an active metal salt solution into the carrier, simultaneously dropwise adding an alkali solution into the carrier for coprecipitation, filtering, roasting the carrier for 1 to 20 hours at the temperature of between 500 and 800 ℃ in a nitrogen atmosphere, and cooling the carrier to the room temperature to obtain a supported catalyst precursor;
3) And (3) reducing the supported catalyst precursor in a hydrogen atmosphere to obtain the hydrogenation catalyst.
3. The method of claim 2, wherein the active metal salts are ruthenium chloride and molybdenum chloride.
4. The method according to claim 2, wherein in the step 3), the reduction temperature is 70 ℃ to 200 ℃ and the reduction time is 2 to 25 hours.
5. The method according to claim 2, wherein in the step 3), the reduction temperature is 100-150 ℃ and the reduction time is 5-10 hours.
6. The method according to claim 1, wherein the addition amount of the hydrogenation catalyst is 0.5-5% of the mass of the crude diol.
7. The method according to claim 1, wherein in the hydrogenation reaction, the reaction temperature is 60-150 ℃, the reaction pressure is 0.1-10 Mpa, and the reaction time is 2-24 h.
8. The method according to claim 1, wherein in the hydrogenation reaction, the reaction temperature is 80-100 ℃, the reaction pressure is 1-5 Mpa, and the reaction time is 5-10 h.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1463994A (en) * 1973-12-11 1977-02-09 Chevron Res Oxo-related reaction for the production of triols and diols
WO2007125909A1 (en) * 2006-04-28 2007-11-08 Kuraray Co., Ltd. Method for production of 3-methyl-1,5-pentanediol
WO2015152066A1 (en) * 2014-03-31 2015-10-08 株式会社クラレ Polyester polyol having superior durability
CN109400452A (en) * 2017-08-18 2019-03-01 中国科学院大连化学物理研究所 A kind of method that furan derivatives acid catalysis adds hydrogen 3- acetylpropyl alcohol and 1,4- pentanediol
WO2020192477A1 (en) * 2019-03-22 2020-10-01 浙江新和成股份有限公司 Catalyst and method for preparing isopentyl diol

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1463994A (en) * 1973-12-11 1977-02-09 Chevron Res Oxo-related reaction for the production of triols and diols
WO2007125909A1 (en) * 2006-04-28 2007-11-08 Kuraray Co., Ltd. Method for production of 3-methyl-1,5-pentanediol
WO2015152066A1 (en) * 2014-03-31 2015-10-08 株式会社クラレ Polyester polyol having superior durability
CN109400452A (en) * 2017-08-18 2019-03-01 中国科学院大连化学物理研究所 A kind of method that furan derivatives acid catalysis adds hydrogen 3- acetylpropyl alcohol and 1,4- pentanediol
WO2020192477A1 (en) * 2019-03-22 2020-10-01 浙江新和成股份有限公司 Catalyst and method for preparing isopentyl diol

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