CN111018667B - Green method for preparing butanol and octanol by hydrogenation catalyst - Google Patents

Green method for preparing butanol and octanol by hydrogenation catalyst Download PDF

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CN111018667B
CN111018667B CN201911354916.6A CN201911354916A CN111018667B CN 111018667 B CN111018667 B CN 111018667B CN 201911354916 A CN201911354916 A CN 201911354916A CN 111018667 B CN111018667 B CN 111018667B
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butanol
octanol
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catalyst
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CN111018667A (en
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崔课贤
楚庆岩
周立亮
杨彬
郭振兴
杨震
缪金帅
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Zibo Nalcohol Chemical Co ltd
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Zibo Nalcohol Chemical 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
    • C07C29/132—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
    • C07C29/136—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
    • C07C29/14—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 a —CHO group
    • C07C29/141—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 a —CHO group with hydrogen or hydrogen-containing gases
    • 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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
    • 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
    • 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
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
    • C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency

Abstract

The invention relates to a green method for preparing butanol and octanol, in particular to a green method for preparing butanol and octanol by using a hydrogenation catalyst. Taking butyl octanol residual liquid and butyl octanol residual liquid as raw materials, firstly carrying out primary distillation pretreatment to obtain primary distillation, mixing and preheating the primary distillation, then entering a catalytic rectifying tower for catalytic hydrogenation reaction, filling a monatomic palladium catalyst in the catalytic rectifying tower, and extracting a reaction product from a tower kettle of the catalytic rectifying tower to obtain butyl octanol; wherein: the monoatomic palladium catalyst is prepared by taking alumina as a carrier and utilizing a light deposition method. According to the preparation method, the monatomic palladium catalyst is prepared, metal is uniformly dispersed on the carrier in a monatomic form, so that the catalyst has excellent catalytic performance, and the active sites of the monatomic catalyst are exposed more, so that the catalytic hydrogenation efficiency is obviously enhanced; the invention prepares high-purity butanol and octanol by adopting proper process and conditions, the product purity of the invention is more than or equal to 98.8 percent, and the single yield is more than or equal to 99.1 percent.

Description

Green method for preparing butanol and octanol by hydrogenation catalyst
Technical Field
The invention relates to a green method for preparing butanol and octanol, in particular to a green method for preparing butanol and octanol by using a hydrogenation catalyst.
Background
Butanol and octanol are conventionally referred to as butanol and octanol because they can be produced in the same set of equipment by the hydroxyl synthesis method. The butyl octanol is colorless transparent flammable oily liquid. Butanol and octanol are important raw materials for synthesizing fine chemical products, and are mainly used for producing plasticizers, solvents, dehydrating agents, defoaming agents, dispersing agents, flotation agents, petroleum additives, synthetic spices and the like.
Butanol is a new biofuel with great potential, called second generation biofuel. The advantages of biobutanol as a new biofuel are: compared with transportation fuel from petroleum refining, the fuel has remarkable environmental benefit, and does not generate SO when being combustedXOr NOXAnd can reduce the environmental emission of greenhouse gases. Compared with the existing biofuel, the biological butanol is resistant to water pollution in the gasoline blend, can achieve higher mixing ratio with the gasoline, and does not need to modify vehicles. Compared with ethanol mixed gasoline, the butanol has low vapor pressure, can flow through a pipeline, has large tolerance to water as an impurity when being mixed with the gasoline, has higher economic efficiency, and can improve the fuel efficiency and the driving mileage of a vehicle. There are 3 methods for industrially producing butanol: a oxo synthesis method. Propylene with CO, H2Under the condition of pressure and heating and in the presence of catalyst the n-butyl alcohol and isobutyraldehyde are synthesized by carbonyl synthesis, and after hydrogenation the n-butyl alcohol is obtained by fractionation, so that it is a main method for industrially producing butanol. ② fermentation method. Taking starch and the like as raw materials, inoculating an acetone-butanol strain, performing Acetone Butanol (ABE) fermentation, and rectifying fermentation liquor to obtain a product of n-butanol. And thirdly, aldol condensation method. Condensing acetaldehyde into butyraldehyde, dehydrating to generate crotonaldehyde, and hydrogenating to obtain n-butanol. The industry for the fermentative production of acetone and butanol began in 1913. After the first world war outbreak, the use of acetone for manufacturing explosives and aircraft wing coatings, etc. has exploded. In the UK, an alcohol plant is firstly transformed into an acetone-butanol plant, then branch plants are built around the world, and the acetone and butanol are produced in a large scale by taking corn as a raw material. After a war, because about 2 times of n-butanol is prepared simultaneously with acetone, no available value is found, the acetone and butanol industry has declined and stopped, and when the n-butanol is found to be the best solvent for preparing butyl acetate as nitrocellulose, the industry obtains new growth. In the fifties and sixties of the 20 th century, the acetone and butanol fermentation industry declined due to competition from petrochemical industry. However, the oil crisis in the 70 s prompted people to realize the fermentation of acetone and butanolIndustrial importance.
Octanol is mainly used for preparing phthalate and aliphatic dibasic acid ester plasticizers, such as dioctyl phthalate, dioctyl azelate, dioctyl sebacate and the like, is respectively used as a main plasticizer and a cold-resistant auxiliary plasticizer of plastics, a defoaming agent, a dispersing agent, a mineral separation agent and a petroleum additive, and is also used for printing and dyeing, paints, films and the like. In the field of plasticizers, octanol generally refers to 2-ethyl ethanol, a bulk material on the million ton scale, which is far more valuable industrially than n-octanol. Octanol is also used as a fragrance per se, blended with floral essences such as rose, lily, etc., as a soap fragrance. The product is edible spice which is specified as allowed in GB2760-86 of China. The method is mainly used for preparing essence of coconut, pineapple, peach, chocolate and citrus, and is used as a surfactant, a solvent, a defoaming agent, an industrial auxiliary agent and the like. The octanol is prepared by the following three methods: coconut oil or palm kernel oil is used as raw material. High-pressure hydrogenation is carried out on coconut oil in the presence of a Cu-Cr catalyst, and the obtained product is refined through rectification under reduced pressure to obtain octanol with high purity; ethylene is taken as a raw material; butadiene is used as a raw material, and the butadiene is hydrated and dimerized to prepare octanol.
The methods for preparing butanol and octanol have the problems of high raw material cost, complex preparation process and the like.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a green method for preparing butanol and octanol by using a hydrogenation catalyst, which comprises the steps of firstly preparing a monatomic palladium catalyst, uniformly dispersing metal on a carrier in a monatomic form to form a catalyst with excellent catalytic performance, and obviously enhancing the catalytic hydrogenation efficiency; the green method for preparing butanol and octanol by using the hydrogenation catalyst provided by the invention is used for rectifying to obtain high-purity butanol and octanol by selecting a proper process and conditions, and is high in product purity and single yield.
The green method for preparing the butanol and the octanol by using the hydrogenation catalyst comprises the steps of taking butanol and octanol residual liquid as raw materials, firstly carrying out primary distillation pretreatment to obtain primary distillation, mixing and preheating the primary distillation, then entering a catalytic rectifying tower for catalytic hydrogenation reaction, filling a monatomic palladium catalyst in the catalytic rectifying tower, and extracting a reaction product from a tower kettle of the catalytic rectifying tower to obtain the butanol and the octanol; wherein: the monoatomic palladium catalyst is prepared by taking alumina as a carrier and palladium chloride as a raw material by a photo-deposition method.
The preliminary distillation pretreatment is a three-tower continuous treatment process of a butyraldehyde tower, a butanol tower and an octenal tower; the operation flow of the preliminary distillation pretreatment is as follows: the residual liquid of butanol and octanol is controlled by heating steam and reflux in a butyraldehyde tower, the heating temperature of the butyraldehyde tower is controlled to be 85-95 ℃, the reflux ratio is 0.5-1.0, high-purity butyraldehyde is separated, and the tower bottom component enters the butyraldehyde tower; controlling the heating temperature of the butanol tower to be 115-125 ℃ and the reflux ratio to be 0.5-1.0 by controlling steam and reflux in the butanol tower, and separating out high-purity butanol; the components at the bottom of the butanol tower enter an octenal tower, part of heavy components are separated out and sent to a recovery tank area, and the materials at the top end enter the octenal tower; rectifying in an octenal tower to obtain octenal at the tower top, and feeding the tower bottom components into a recovery tank area; and collecting butanol obtained after three-tower continuous treatment as a product, and mixing the obtained butyraldehyde and octenal to obtain a primary fraction.
The butanol tower and the octenal tower adopt decompression operation, and the decompression pressure range is as follows: 0.3-0.6 MPa.
The butyl alcohol and octanol residual liquid comprises the following main components: mixed solution of butyraldehyde, octenal, butanol and octanol; wherein, the weight percentage of butyraldehyde is 11-12%, octenal is 28-43%, butanol is 17-25%, and octanol is 8-12%.
As a preferred technical scheme, the preparation method of the monatomic palladium catalyst is as follows:
(1) adding deionized water into a stirring reactor, heating to 60-82 ℃, adding a sodium sulfate solution, adding aluminum sulfate under stirring, stopping feeding aluminum sulfate when the pH value of the solution reaches 3.5-4.2, and aging the solution; then filtering, forming and drying to obtain the spherical Al2O3A carrier;
(2) spheroidal Al2O3Adding deionized water and glycol solution into the carrier, placing the carrier in an ultrasonic stirrer, and ultrasonically stirring for 13-17min to form uniformly dispersed suspension; adding palladium chloride into the suspensionThe solution is directly irradiated for a period of time by turning on a xenon lamp light source; washing, centrifuging, and drying overnight to obtain the monatomic palladium catalyst.
The volume ratio of the deionized water to the sodium sulfate solution in the step (1) is 8-12: 1, the aging time is 11-13 h.
In the step (2): spherical Al2O3The molar ratio of the carrier, palladium chloride, deionized water and glycol is 1-1.02: 1-2: 3-4: 0.1-0.2; the time for directly irradiating by turning on the xenon lamp light source is 0.8-1.2 h.
Before the catalytic hydrogenation reaction is started, a monatomic palladium catalyst is filled in the middle of a rectifying tower, and H is introduced2Reacting for 4-4.2h, and reducing the II-valence palladium in the monoatomic palladium catalyst into a metallic valence state. The meaning of this step is to reduce the valence II metal in the catalyst component to 0 valence, if a batch of catalyst is always used, it is not necessary to introduce H every time2。
The reflux ratio of the catalytic rectifying tower is 0.5-1.0; the bottom temperature of the catalytic rectifying tower is 50-90 ℃; the top temperature of the catalytic rectifying tower is 30-70 ℃; the absolute pressure at the top of the catalytic rectifying tower is 0.04-0.3 MPa; the absolute pressure at the bottom is 0.50-2.0 MPa.
The invention relates to a green method for preparing butanol and octanol by using a hydrogenation catalyst, which comprises the following steps of: 2-2.6: 1-1.4, preheating to 60 +/-5 ℃, feeding in a feeding system in the middle of a catalytic distillation tower, filling a monoatomic palladium catalyst in a distillation section of the catalytic distillation tower, wherein the dosage of the catalyst is 0.28-0.32% of the mass of the added initial fraction, after the reaction is finished, feeding butanol and octanol components into a stripping section, extracting by a tower kettle, and obtaining high-purity butanol and octanol after the separation is finished.
Compared with the prior art, the invention has the following advantages:
(1) according to the monatomic palladium catalyst prepared by the method, metal is uniformly dispersed on the carrier in a monatomic form, so that the catalyst has excellent catalytic performance, and the active sites of the monatomic palladium catalyst are exposed more, so that the catalytic hydrogenation efficiency is remarkably enhanced.
(2) The green method for preparing the butanol and the octanol by the hydrogenation catalyst is a heterogeneous catalysis reaction rectification reaction, integrates the heterogeneous catalysis reaction and the rectification separation, strengthens the reaction and the separation by the coupling of the separation and the reaction, has the advantages of low consumption, low investment and the like, and is advanced in process and relatively simple in operation.
(3) The method for preparing the butanol and the octanol waste liquid provided by the invention utilizes a three-tower sequential cutting process to completely separate the components in the mother liquid, thereby realizing the efficient utilization of the waste liquid.
(4) The invention relates to a green method for preparing butanol and octanol by catalytic distillation, which is used for preparing a monatomic palladium catalyst with high catalytic activity, realizes simultaneous reaction and separation by using a catalytic distillation method, extracts a reaction product from a tower kettle by using the catalytic distillation method, and obtains the butanol and octanol with high purity by further distillation, wherein the purity of the product is more than or equal to 98.8 percent, and the single yield is more than or equal to 99.1 percent.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
The preparation method of the monoatomic palladium catalyst comprises the following steps: placing 100ml of deionized water at the bottom of a stirring reactor, heating to 70 ℃, adding 10ml of sodium sulfate solution, adding 20g of aluminum sulfate in the process of continuously stirring, stopping feeding when the pH value reaches 4.2, and aging overnight at room temperature; then filtering, washing, forming and drying to obtain the spherical Al2O3A carrier; weigh 10g of prepared spherical Al2O3Putting the carrier into a 400ml quartz beaker, then adding 200ml deionized water and 10ml ethylene glycol solution, ultrasonically stirring for 15min, adding 0.1g palladium chloride solution, turning on a xenon lamp light source to directly irradiate the quartz beaker for 1h, washing with deionized water, centrifuging for 3 times, and drying at 30 ℃ for 3h to obtain the monatomic palladium catalyst.
The preliminary distillation pretreatment is a three-tower continuous treatment process of a butyraldehyde tower, a butanol tower and an octenal tower; the operation flow of the preliminary distillation pretreatment is as follows: the residual liquid of butanol and octanol is controlled by heating steam and reflux in a butyraldehyde tower, the heating temperature of the butyraldehyde tower is controlled to be 90 ℃, the reflux ratio is 0.6, high-purity butyraldehyde is separated, and the tower bottom component enters the butyraldehyde tower; controlling the heating temperature of the butanol tower to be 120 ℃ and the reflux ratio to be 0.6 by controlling steam and reflux in the butanol tower, and separating out high-purity butanol; the components at the bottom of the butanol tower enter an octenal tower, part of heavy components are separated out and sent to a recovery tank area, and the materials at the top end enter the octenal tower; rectifying in an octenal tower to obtain octenal at the tower top, and feeding the tower bottom components into a recovery tank area; collecting butanol obtained after three-tower continuous treatment as a product, and mixing the obtained butyraldehyde and octenal to obtain a primary fraction; wherein: the butanol tower and the octenal tower adopt decompression operation, and the decompression pressure range is as follows: 0.5 MPa.
A green method for preparing butanol and octanol by using a hydrogenation catalyst comprises the following steps of (1): 2: 1 is preheated to 60 ℃ and then fed into a feeding system in the middle of a catalytic rectification tower, the monoatomic palladium catalyst is filled in a rectification section of the catalytic rectification tower, the dosage of the catalyst is 0.3 percent of the mass of the added initial fraction, the temperature of the bottom of a reactor of the catalytic rectification tower is 70 ℃, and the absolute pressure is 0.6 MPa; the top temperature was 50 ℃, the absolute pressure was 0.15MPa, and the reflux ratio was 0.6. After the reaction is finished, the butanol and octanol components enter a stripping section, are extracted through a tower kettle, and after the separation is finished, the target product butanol and octanol is obtained, wherein the product yield is 99.5%, and the purity is 99.5%.
Example 2
The preparation method of the monoatomic palladium catalyst comprises the following steps: placing 100ml of deionized water at the bottom of a stirring reactor, heating to 80 ℃, adding 10ml of sodium sulfate solution, adding 20g of aluminum sulfate in the process of continuously stirring, stopping feeding when the pH value reaches 3.8, and aging overnight at room temperature; then filtering, washing, forming and drying to obtain the spherical Al2O3A carrier; weighing 1.5g of prepared carrier, putting the carrier into a 400ml quartz beaker, adding 200ml of deionized water and 10ml of ethylene glycol solution, ultrasonically stirring for 15min, adding 0.12g of palladium chloride solution, turning on a xenon lamp light source to directly irradiate the quartz beaker for 1h, washing with deionized water, centrifuging for 3 times, and drying at 30 ℃ for 3h to obtain the monatomic palladium catalyst.
The preliminary distillation pretreatment is a three-tower continuous treatment process of a butyraldehyde tower, a butanol tower and an octenal tower; the operation flow of the preliminary distillation pretreatment is as follows: the residual liquid of butanol and octanol is controlled by heating steam and reflux in a butyraldehyde tower, the heating temperature of the butyraldehyde tower is controlled to be 95 ℃, the reflux ratio is 0.8, high-purity butyraldehyde is separated, and the tower bottom component enters the butyraldehyde tower; controlling the heating temperature of the butanol tower to be 116 ℃ and the reflux ratio to be 0.8 by controlling steam and reflux in the butanol tower, and separating out high-purity butanol; the components at the bottom of the butanol tower enter an octenal tower, part of heavy components are separated out and sent to a recovery tank area, and the materials at the top end enter the octenal tower; rectifying in an octenal tower to obtain octenal at the tower top, and feeding the tower bottom components into a recovery tank area; collecting butanol obtained after three-tower continuous treatment as a product, and mixing the obtained butyraldehyde and octenal to obtain a primary fraction; wherein: the butanol tower and the octenal tower adopt decompression operation, and the decompression pressure range is as follows: 0.4 MPa.
A green method for preparing butanol and octanol by using a hydrogenation catalyst comprises the following steps of (1.4) according to a molar ratio of the initial fraction to hydrogen to nitrogen: 2: 1 is preheated to 60 ℃ and then fed into a feeding system in the middle of a catalytic rectification tower, the monoatomic palladium catalyst is filled in a rectification section of the catalytic rectification tower, the dosage of the catalyst is 0.3 percent of the mass of the added initial fraction, the bottom temperature of a reactor of the catalytic rectification tower is 60 ℃, and the absolute pressure is 0.8 MPa; the top temperature was 40 ℃, the absolute pressure 0.2MPa, and the reflux ratio 0.7. After the reaction is finished, the butanol and octanol components enter a stripping section, are extracted by a tower kettle, and after separation is finished, the target product butanol and octanol are obtained, wherein the product yield is 99.5%, and the purity is 99.3%.
Example 3
The preparation method of the monoatomic palladium catalyst comprises the following steps: placing 100ml of deionized water at the bottom of a stirring reactor, heating to 80 ℃, adding 10ml of sodium sulfate solution, adding 20g of aluminum sulfate in the process of continuously stirring, stopping feeding when the pH value is tested to be 3.6, and aging at room temperature overnight; then filtering, washing, forming and drying to obtain the spherical Al2O3A carrier; weighing 1.5g of the prepared carrier, putting the carrier into a 400ml quartz beaker, adding 200ml of deionized water and 10ml of ethylene glycol solution, ultrasonically stirring for 15min, adding 0.12g of palladium chloride solution, turning on a xenon lamp light source to directly irradiate the quartz beaker for 1h, washing with deionized water, centrifuging for 3 times,and drying at 30 ℃ for 3h to obtain the monatomic palladium catalyst.
A green method for preparing butanol and octanol by using a hydrogenation catalyst comprises the following steps of mixing the initial fraction obtained in example 1, hydrogen and nitrogen in a molar ratio of 1.2: 2: 1 is preheated to 60 ℃ and then fed into a feeding system in the middle of a catalytic rectification tower, the monoatomic palladium catalyst is filled in a rectification section of the catalytic rectification tower, the dosage of the catalyst is 0.31 percent of the mass of the added initial fraction, the bottom temperature of a reactor of the catalytic rectification tower is 80 ℃, and the absolute pressure is 1.0 MPa; the top temperature was 60 ℃, the absolute pressure was 0.1MPa, and the reflux ratio was 0.8. After the reaction is finished, the butanol and octanol components enter a stripping section, are extracted through a tower kettle, and after the separation is finished, the target product butanol and octanol is obtained, wherein the product yield is 99.2%, and the purity is 99.4%.
Example 4
The preparation method of the monoatomic palladium catalyst comprises the following steps: placing 100ml of deionized water at the bottom of a stirring reactor, heating to 82 ℃, adding 10ml of sodium sulfate solution, adding 20g of aluminum sulfate in the process of continuously stirring, stopping feeding when the pH value reaches 3.9, and aging overnight at room temperature; then filtering, washing, forming and drying to obtain the spherical Al2O3A carrier; weighing 1.8g of prepared carrier, putting the carrier into a 400ml quartz beaker, adding 200ml of deionized water and 10ml of ethylene glycol solution, ultrasonically stirring for 15min, adding 0.12g of palladium chloride solution, turning on a xenon lamp light source to directly irradiate the quartz beaker for 1h, washing with deionized water, centrifuging for 3 times, and drying at 30 ℃ for 3h to obtain the monatomic palladium catalyst.
A green method for preparing butanol and octanol by using a hydrogenation catalyst comprises the following steps of mixing the initial fraction obtained in example 1, hydrogen and nitrogen according to a molar ratio of 1.4: 2.1: 1 is preheated to 60 ℃ and then fed into a feeding system in the middle of a catalytic rectification tower, the monoatomic palladium catalyst is filled in a rectification section of the catalytic rectification tower, the dosage of the catalyst is 0.3 percent of the mass of the added initial fraction, the bottom temperature of a reactor of the catalytic rectification tower is 50 ℃, and the absolute pressure is 1.2 MPa; the top temperature was 30 ℃, the absolute pressure was 0.1MPa, and the reflux ratio was 0.9. After the reaction is finished, the butanol and octanol components enter a stripping section, are extracted through a tower kettle, and after the separation is finished, the target product butanol and octanol is obtained, wherein the product yield is 99.4%, and the purity is 99.2%.
Example 5
A green method for preparing butanol and octanol by using a hydrogenation catalyst is characterized in that the primary fraction obtained in example 1, hydrogen and nitrogen are mixed according to a molar ratio of 1.3: 2.2: the proportion of 1 is preheated to 60 ℃ and then fed into a feeding system at the middle part of a catalytic rectification tower, the monoatomic palladium catalyst prepared in the embodiment 1 is filled in a rectification section of the catalytic rectification tower, the using amount of the catalyst is 0.3 percent of the mass of the added initial fraction, the bottom temperature of a reactor of the catalytic rectification tower is 60 ℃, and the absolute pressure is 0.6 MPa; the top temperature was 50 ℃, the absolute pressure was 0.04MPa, and the reflux ratio was 0.6. After the reaction is finished, the butanol and octanol components enter a stripping section, are extracted through a tower kettle, and after the separation is finished, the target product butanol and octanol is obtained, wherein the product yield is 99.5%, and the purity is 98.8%.
Example 6
A green method for preparing butanol and octanol by using a hydrogenation catalyst comprises the following steps of mixing the initial fraction obtained in example 1, hydrogen and nitrogen in a molar ratio of 1.2: 2.6: the proportion of 1 is preheated to 60 ℃ and then fed into a feeding system at the middle part of a catalytic rectification tower, the monoatomic palladium catalyst prepared in the embodiment 1 is filled in a rectification section of the catalytic rectification tower, the using amount of the catalyst is 0.32 percent of the mass of the added initial fraction, the bottom temperature of a reactor of the catalytic rectification tower is 90 ℃, and the absolute pressure is 0.6 MPa; the top temperature was 70 ℃, the absolute pressure was 0.3MPa, and the reflux ratio was 0.6. After the reaction is finished, the butanol and octanol components enter a stripping section, are extracted through a tower kettle, and after the separation is finished, the target product butanol and octanol is obtained, wherein the product yield is 99.2%, and the purity is 99.1%.
Example 7
A green method for preparing butanol and octanol by using a hydrogenation catalyst comprises the following steps of mixing the initial fraction obtained in example 1, hydrogen and nitrogen in a molar ratio of 1.3: 2: the proportion of 1 is preheated to 60 ℃ and then fed into a feeding system at the middle part of a catalytic rectification tower, the monoatomic palladium catalyst prepared in the embodiment 1 is filled in a rectification section of the catalytic rectification tower, the using amount of the catalyst is 0.3 percent of the mass of the added initial fraction, the bottom temperature of a reactor of the catalytic rectification tower is 60 ℃, and the absolute pressure is 0.6 MPa; the top temperature was 50 ℃, the absolute pressure was 0.1MPa, and the reflux ratio was 0.6. After the reaction is finished, the butanol and octanol components enter a stripping section, are extracted through a tower kettle, and after the separation is finished, the target product butanol and octanol is obtained, wherein the product yield is 99.3%, and the purity is 98.9%.
Example 8
A green method for preparing butanol and octanol by using a hydrogenation catalyst comprises the following steps of mixing the initial fraction obtained in example 1, hydrogen and nitrogen in a molar ratio of 1.5: 2: 1 is preheated to 60 ℃ and then fed into a feeding system in the middle of a catalytic rectifying tower, the monoatomic palladium catalyst prepared in the embodiment 1 is filled in a rectifying section of the catalytic rectifying tower, the using amount of the catalyst is 0.29 percent of the mass of the added initial fraction, the bottom temperature of a reactor of the catalytic rectifying tower is 70 ℃, and the absolute pressure is 2.0 MPa; the top temperature was 50 ℃, the absolute pressure was 0.2MPa, and the reflux ratio was 0.6. After the reaction is finished, the butanol and octanol components enter a stripping section, are extracted through a tower kettle, and after the separation is finished, the target product butanol and octanol is obtained, wherein the product yield is 99.2%, and the purity is 99.2%.
Example 9
A green method for preparing butanol and octanol by using a hydrogenation catalyst is characterized in that the primary fraction obtained in example 1, hydrogen and nitrogen are mixed according to a molar ratio of 1.1: 2: the proportion of 1 is preheated to 60 ℃ and then fed into a feeding system at the middle part of a catalytic rectification tower, the monoatomic palladium catalyst prepared in the embodiment 1 is filled in a rectification section of the catalytic rectification tower, the using amount of the catalyst is 0.3 percent of the mass of the added initial fraction, the bottom temperature of a reactor of the catalytic rectification tower is 60 ℃, and the absolute pressure is 0.5 MPa; the top temperature was 50 ℃, the absolute pressure was 0.14MPa, and the reflux ratio was 0.6. After the reaction is finished, the butanol and octanol components enter a stripping section, are extracted through a tower kettle, and after the separation is finished, the target product butanol and octanol is obtained, wherein the product yield is 99.1%, and the purity is 99.3%.
Example 10
A green method for preparing butanol and octanol by using a hydrogenation catalyst comprises the following steps of mixing the initial fraction obtained in example 1, hydrogen and nitrogen in a molar ratio of 1.6: 2: 1 is preheated to 60 ℃ and then fed into a feeding system in the middle of a catalytic rectification tower, the monoatomic palladium catalyst prepared in the example 1 is filled in a rectification section of the catalytic rectification tower, the dosage of the catalyst is 0.3 percent of the mass of the added initial fraction, the bottom temperature of a reactor of the catalytic rectification tower is 65 ℃, and the absolute pressure is 1.5 MPa; the top temperature was 55 ℃, the absolute pressure was 0.25MPa, and the reflux ratio was 0.6. After the reaction is finished, the butanol and octanol components enter a stripping section, are extracted through a tower kettle, and after the separation is finished, the target product butanol and octanol is obtained, wherein the product yield is 99.2%, and the purity is 98.9%.
Example 11
A green method for preparing butanol and octanol by using a hydrogenation catalyst is characterized in that the primary fraction obtained in example 1, hydrogen and nitrogen are mixed according to a molar ratio of 1.2: 2: the raw materials are preheated to 60 ℃ and then fed into a feeding system in the middle of a catalytic rectification tower, the monoatomic palladium catalyst prepared in the example 1 is filled in a rectification section of the catalytic rectification tower, the using amount of the catalyst is 0.28 percent of the mass of the added initial fraction, the bottom temperature of a reactor of the catalytic rectification tower is 60 ℃, and the absolute pressure is 1.0 MPa; the top temperature was 50 ℃, the absolute pressure was 0.15MPa, and the reflux ratio was 1.0. After the reaction is finished, the butanol and octanol components enter a stripping section, are extracted through a tower kettle, and after the separation is finished, the target product butanol and octanol is obtained, wherein the product yield is 99.1%, and the purity is 99.4%.
Example 12
A green method for preparing butanol and octanol by using a hydrogenation catalyst comprises the following steps of mixing the initial fraction obtained in example 1, hydrogen and nitrogen according to a molar ratio of 1: 2: the proportion of 1 is preheated to 60 ℃ and then fed into a feeding system at the middle part of a catalytic rectification tower, the monoatomic palladium catalyst prepared in the embodiment 1 is filled in a rectification section of the catalytic rectification tower, the using amount of the catalyst is 0.3 percent of the mass of the added initial fraction, the bottom temperature of a reactor of the catalytic rectification tower is 60 ℃, and the absolute pressure is 0.6 MPa; the top temperature was 50 ℃, the absolute pressure was 0.08MPa, and the reflux ratio was 0.6. After the reaction is finished, the butanol and octanol components enter a stripping section, are extracted through a tower kettle, and after the separation is finished, the target product butanol and octanol is obtained, wherein the product yield is 99.4%, and the purity is 98.8%.
Example 13
A green method for preparing butanol and octanol by using a hydrogenation catalyst comprises the following steps of mixing the initial fraction obtained in example 1, hydrogen and nitrogen according to a molar ratio of 1: 2.4: 1 is preheated to 60 ℃ and then fed into a feeding system in the middle of a catalytic rectification tower, the monoatomic palladium catalyst prepared in the example 1 is filled in a rectification section of the catalytic rectification tower, the dosage of the catalyst is 0.3 percent of the mass of the added initial fraction, the bottom temperature of a reactor of the catalytic rectification tower is 75 ℃, and the absolute pressure is 1.2 MPa; the top temperature was 60 ℃, the absolute pressure was 0.2MPa, and the reflux ratio was 0.6. After the reaction is finished, the butanol and octanol components enter a stripping section, are extracted through a tower kettle, and after the separation is finished, the target product butanol and octanol is obtained, wherein the product yield is 99.3%, and the purity is 99.1%.
Example 14
A green method for preparing butanol and octanol by using a hydrogenation catalyst comprises the following steps of mixing the initial fraction obtained in example 1, hydrogen and nitrogen according to a molar ratio of 1: 2.2: 1 is preheated to 60 ℃ and then fed into a feeding system in the middle of a catalytic rectifying tower, the monoatomic palladium catalyst prepared in the embodiment 1 is filled in a rectifying section of the catalytic rectifying tower, the using amount of the catalyst is 0.3 percent of the mass of the added initial fraction, the bottom temperature of a reactor of the catalytic rectifying tower is 60 ℃, and the absolute pressure is 0.6 MPa; the top temperature was 50 ℃, the absolute pressure was 0.2MPa, and the reflux ratio was 0.5. After the reaction is finished, the butanol and octanol components enter a stripping section, are extracted through a tower kettle, and after the separation is finished, the target product butanol and octanol is obtained, wherein the product yield is 99.3%, and the purity is 98.9%.
Example 15
A green method for preparing butanol and octanol by using a hydrogenation catalyst comprises the following steps of mixing the initial fraction obtained in example 1, hydrogen and nitrogen according to a molar ratio of 1: 2: 1.4, preheating to 60 ℃, feeding in a feeding system in the middle of a catalytic rectification tower, and filling the monoatomic palladium catalyst prepared in the example 1 in a rectification section of the catalytic rectification tower, wherein the using amount of the catalyst is 0.3 percent of the mass of the added initial fraction, the bottom temperature of a reactor of the catalytic rectification tower is 80 ℃, and the absolute pressure is 1.5 MPa; the top temperature was 60 ℃, the absolute pressure was 0.3MPa, and the reflux ratio was 0.6. After the reaction is finished, the butanol and octanol components enter a stripping section, are extracted through a tower kettle, and after the separation is finished, the target product butanol and octanol is obtained, wherein the product yield is 99.2%, and the purity is 99.6%.
Example 16
A green method for preparing butanol and octanol by using a hydrogenation catalyst is characterized in that the primary fraction obtained in example 1, hydrogen and nitrogen are mixed according to a molar ratio of 1: 2: 1.2, preheating to 60 ℃, feeding in a feeding system in the middle of a catalytic rectification tower, and filling the monoatomic palladium catalyst prepared in the example 1 in a rectification section of the catalytic rectification tower, wherein the using amount of the catalyst is 0.3 percent of the mass of the added initial fraction, the bottom temperature of a reactor of the catalytic rectification tower is 80 ℃, and the absolute pressure is 0.7 MPa; the top temperature was 50 ℃, the absolute pressure was 0.1MPa, and the reflux ratio was 0.5. After the reaction is finished, the butanol and octanol components enter a stripping section, are extracted through a tower kettle, and after the separation is finished, the target product butanol and octanol is obtained, wherein the product yield is 989%, and the purity is 98.9%.
Example 17
A green method for preparing butanol and octanol by using a hydrogenation catalyst comprises the following steps of mixing the initial fraction obtained in example 1, hydrogen and nitrogen according to a molar ratio of 1: 2.5: the proportion of 1 is preheated to 60 ℃ and then fed into a feeding system at the middle part of a catalytic rectification tower, the monoatomic palladium catalyst prepared in the embodiment 1 is filled in a rectification section of the catalytic rectification tower, the using amount of the catalyst is 0.3 percent of the mass of the added initial fraction, the bottom temperature of a reactor of the catalytic rectification tower is 60 ℃, and the absolute pressure is 0.9 MPa; the top temperature was 45 ℃, the absolute pressure was 0.04MPa, and the reflux ratio was 0.6. After the reaction is finished, the butanol and octanol components enter a stripping section, are extracted by a tower kettle, and after separation is finished, the target product butanol and octanol are obtained, wherein the product yield is 99.3%, and the purity is 99.1%.
Example 18
A green method for preparing butanol and octanol by using a hydrogenation catalyst comprises the following steps of mixing the initial fraction obtained in example 1, hydrogen and nitrogen according to a molar ratio of 1: 2: 1 is preheated to 60 ℃ and then fed into a feeding system in the middle of a catalytic rectification tower, the monoatomic palladium catalyst prepared in the example 1 is filled in a rectification section of the catalytic rectification tower, the dosage of the catalyst is 0.3 percent of the mass of the added initial fraction, the bottom temperature of a reactor of the catalytic rectification tower is 70 ℃, and the absolute pressure is 0.6 MPa; the top temperature was 40 ℃, the absolute pressure was 0.1MPa, and the reflux ratio was 0.7. After the reaction is finished, the butanol and octanol components enter a stripping section, are extracted by a tower kettle, and after separation is finished, the target product butanol and octanol are obtained, wherein the product yield is 99.4%, and the purity is 99.3%.
Comparative example 1
The comparative example 1 is the same as the example 1 in raw material and preparation method, and is different in that a single-atom palladium catalyst is replaced by a supported nano-palladium catalyst, a catalytic rectification tower is replaced by a common reactor, the common reactor is a normal-pressure reaction, the temperature is 80 +/-5 ℃, after the reaction is finished, the target product butanol and octanol are obtained through rectification separation, the product yield is 90.7%, and the purity is 93.3%.
Comparative example 2
The comparative example 2 is the same as the example 2 in raw material and preparation method, and is different in that a single-atom palladium catalyst is replaced by a supported nano-palladium catalyst, a catalytic rectification tower is replaced by a common reactor, the common reactor is a normal-pressure reaction, the temperature is 70 +/-5 ℃, after the reaction is finished, the target product butanol and octanol are obtained through rectification separation, the product yield is 90.0%, and the purity is 93.0%.

Claims (7)

1. A green method for preparing butanol and octanol by using a hydrogenation catalyst is characterized by comprising the following steps: taking residual liquid of butyl octanol and residual liquid of octyl alcohol as raw materials, firstly carrying out primary distillation pretreatment to obtain primary distillation, mixing and preheating the primary distillation, then entering a catalytic rectifying tower for catalytic hydrogenation reaction, filling a monatomic palladium catalyst in the catalytic rectifying tower, and extracting a reaction product from a tower kettle of the catalytic rectifying tower to obtain the butyl octanol; wherein: the monoatomic palladium catalyst is prepared by taking alumina as a carrier and palladium chloride as a raw material by a photo-deposition method;
the preparation method of the monoatomic palladium catalyst comprises the following steps:
(1) adding deionized water into a stirring reactor, heating to 60-82 ℃, adding a sodium sulfate solution, adding aluminum sulfate under stirring, stopping feeding aluminum sulfate when the pH value of the solution reaches 3.5-4.2, and aging the solution; then filtering, forming and drying to obtain the spherical Al2O3A carrier;
(2) spheroidal Al2O3Adding deionized water and glycol solution into the carrier, and placing the carrier in an ultrasonic stirrer for ultrasonic stirring for 13-17min to form uniformly dispersed suspension; adding a palladium chloride solution into the suspension, and turning on a xenon lamp light source to directly irradiate for a period of time; washing, centrifuging, and drying in a drying oven overnight to obtain the monatomic palladium catalyst;
in the step (1), the volume ratio of the deionized water to the sodium sulfate solution is 8-12: 1, aging for 11-13 h;
in the step (2): spherical Al2O3The molar ratio of the carrier, palladium chloride, deionized water and glycol is 1-1.02: 1-2: 3-4: 0.1-0.2; the time for directly irradiating by turning on the xenon lamp light source is 0.8-1.2 h.
2. The green process for preparing butanol and octanol using a hydrogenation catalyst according to claim 1, wherein: the preliminary distillation pretreatment is a three-tower continuous treatment process of a butyraldehyde tower, a butanol tower and an octenal tower; the operation flow of the preliminary distillation pretreatment is as follows: the residual liquid of butanol and octanol is controlled by heating steam and reflux in a butyraldehyde tower, the heating temperature of the butyraldehyde tower is controlled to be 85-95 ℃, the reflux ratio is 0.5-1.0, high-purity butyraldehyde is separated, and the tower bottom component enters the butyraldehyde tower; controlling the heating temperature of the butanol tower at 115-125 ℃ and the reflux ratio of 0.5-1.0 by controlling steam and reflux in the butanol tower, and separating out high-purity butanol; the components at the bottom of the butanol tower enter an octenal tower, part of heavy components are separated out and sent to a recovery tank area, and the materials at the top end enter the octenal tower; rectifying in an octenal tower to obtain octenal at the tower top, and feeding the tower bottom components into a recovery tank area; and collecting butanol obtained after three-tower continuous treatment as a product, and mixing the obtained butyraldehyde and octenal to obtain a primary fraction.
3. The green process for preparing butanol and octanol by using the hydrogenation catalyst according to claim 2, wherein: the butanol tower and the octenal tower adopt decompression operation, and the decompression pressure range is as follows: 0.3-0.6 MPa.
4. The green process for preparing butanol and octanol using a hydrogenation catalyst according to claim 1, wherein: the butyl alcohol and octanol residual liquid comprises the following main components: mixed solution of butyraldehyde, octenal, butanol and octanol; wherein: the weight percentage of the butyraldehyde accounts for 11-12%, the octenal accounts for 28-43%, the butanol accounts for 17-25%, and the octanol accounts for 8-12%.
5. The green process for preparing butanol and octanol using hydrogenation catalyst according to claim 1, wherein said catalyst is selected from the group consisting of: before the catalytic hydrogenation reaction is started, a monatomic palladium catalyst is filled in the middle of a rectifying tower, and H is introduced2Reacting for 4-4.2h, and reducing the II-valence palladium in the monoatomic palladium catalyst into a metallic valence state.
6. The green process for preparing butanol and octanol by using the hydrogenation catalyst according to claim 1, wherein: the reflux ratio of the catalytic rectifying tower is 0.5-1.0; the bottom temperature of the catalytic rectifying tower is 50-90 ℃; the top temperature of the catalytic rectifying tower is 30-70 ℃; the absolute pressure at the top of the catalytic rectifying tower is 0.04-0.3 MPa; the absolute pressure at the bottom is 0.50-2.0 MPa.
7. A green process for the preparation of butanol and octanol with a hydrogenation catalyst according to any one of claims 1 to 6, wherein: the primary fraction, hydrogen and nitrogen are mixed according to the mol ratio of 1-1.6: 2-2.6: 1-1.4, preheating to 60 +/-5 ℃, feeding in a feeding system in the middle of a catalytic distillation tower, filling a monoatomic palladium catalyst in a distillation section of the catalytic distillation tower, wherein the dosage of the catalyst is 0.28-0.32% of the mass of the added initial fraction, after the reaction is finished, feeding the butanol and octanol components into a stripping section, extracting the butanol and octanol components through a tower kettle, and obtaining high-purity butanol and octanol components after the separation is finished.
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