CN111018667A - Green method for preparing butanol and octanol by hydrogenation catalyst - Google Patents
Green method for preparing butanol and octanol by hydrogenation catalyst Download PDFInfo
- Publication number
- CN111018667A CN111018667A CN201911354916.6A CN201911354916A CN111018667A CN 111018667 A CN111018667 A CN 111018667A CN 201911354916 A CN201911354916 A CN 201911354916A CN 111018667 A CN111018667 A CN 111018667A
- Authority
- CN
- China
- Prior art keywords
- tower
- butanol
- octanol
- catalytic
- preparing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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%, and the single yield is more than or equal to 99.1%.
Description
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 perfumes 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 NOXCompared with the existing biofuel, the biobutanol is resistant to water pollution in gasoline blends, can reach higher mixing ratio with gasoline without modifying the vehicle, compared with ethanol mixed gasoline, the butanol has low vapor pressure, can flow through a pipeline, has large tolerance to water as impurities when being mixed with the gasoline, has higher economic efficiency of the butanol, can improve the fuel efficiency and the driving mileage of the vehicle, and 3 industrial production methods of the butanol include ① oxo synthesis method, propylene, CO, H and the like2Synthesizing n-isobutyraldehyde and isobutyraldehyde by carbonyl under the conditions of pressurization and heating and in the presence of catalyst, hydrogenating and fractionating to obtain n-butanol, which is the main method for industrially producing butanol ② fermentation method, using starch as raw material, inoculating acetone-butanol strain, making Acetone Butanol (ABE) fermentation, fermenting liquorThe method comprises the steps of obtaining n-butyl alcohol after rectification, ③ aldol condensation method, condensing acetaldehyde into butyraldehyde, dehydrating to obtain crotonaldehyde, and then hydrogenating to obtain n-butyl alcohol, wherein the acetone and butanol production industry by a fermentation method starts in 1913, after the first world outbreak of world war, the use amount of acetone for manufacturing explosives and aviation wing coatings is increased rapidly, British firstly reforms an alcohol plant as an acetone butanol plant, then branch plants are built in various parts of the world, and large-scale production of acetone and butanol is carried out by taking corn as a raw material.
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 the butanol and octanol by the hydrogenation catalyst is characterized in that the appropriate process and conditions are selected, and the high-purity butanol and octanol are obtained through rectification, so that the product purity is high, and the single yield is high.
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 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.
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 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%.
As a preferred technical scheme, 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, placing the carrier in an ultrasonic stirrer, and ultrasonically 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 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 II-valence palladium in the monatomic palladium catalyst into a metallic valence state. The meaning of this step is to reduce the metal of II valence in the catalyst component to 0 valence, if a batch of catalyst is used all the time, 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, simultaneously realizes the simultaneous reaction and separation by utilizing a catalytic distillation method, extracts a reaction product from a tower kettle by utilizing the catalytic distillation method, and further rectifies the reaction product to obtain the butanol and octanol with high purity, 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: 100ml of deionized water is put at the bottom of a stirring reactor and heated to 70 ℃, and 10ml of sulfuric acid is addedAdding 20g of aluminum sulfate into the sodium solution while continuously stirring, stopping feeding when the pH value is tested to be 4.2, and aging at room temperature overnight; 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, adding 200ml deionized water and 10ml ethylene glycol solution, carrying out ultrasonic 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 is tested to be 3.8, and aging at room temperature overnight; 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 was 0.2MPa, and the reflux ratio was 0.7. 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 99.3%.
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 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 is tested to be 3.9, and aging at room temperature overnight; then filtering, washing, forming and drying to obtain the spherical Al2O3A carrier; weigh 1.8g of the prepared support into a 400ml quartz beaker, add 200ml of deionized water and10ml of ethylene glycol solution is ultrasonically stirred for 15min, 0.12g of palladium chloride solution is added, a xenon lamp light source is turned on to directly irradiate a quartz beaker for 1h, the quartz beaker is washed by deionized water and centrifuged for 3 times, and the quartz beaker is dried for 3h at the temperature of 30 ℃ 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 comprises the following steps of mixing the initial fraction obtained in example 1, hydrogen and nitrogen in 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 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 0.29 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 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 comprises the following steps of mixing the initial fraction obtained in example 1, hydrogen and nitrogen in 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 comprises the following steps of mixing the initial fraction obtained in example 1, hydrogen and nitrogen in 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: 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 0.2MPa, 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 comprises the following steps of mixing the initial fraction obtained in example 1, hydrogen and nitrogen according to a molar ratio of 1: 2: 1.2, 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 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 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 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 99.3%.
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 (10)
1. A green method for preparing butanol and octanol by using a hydrogenation catalyst is characterized by comprising the following steps: 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 palladium chloride as a raw material by a photo-deposition method.
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 using a 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 a hydrogenation catalyst according to claim 1, wherein: 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; rear endFiltering, forming and drying to obtain 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 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 overnight to obtain the monatomic palladium catalyst.
6. The green process for preparing butanol and octanol using a hydrogenation catalyst according to claim 5, wherein: 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.
7. The green process for preparing butanol and octanol using a hydrogenation catalyst according to claim 6, wherein: 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.
8. The green process for preparing butanol and octanol using a hydrogenation catalyst according to claim 1, wherein: 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 II-valence palladium in the monatomic palladium catalyst into a metallic valence state.
9. The green process for preparing butanol and octanol using a 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.
10. A green process for the preparation of butanol and octanol with a hydrogenation catalyst according to any one of claims 1 to 9, wherein: the primary fraction, hydrogen and nitrogen are mixed according to a molar 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 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.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201911354916.6A CN111018667B (en) | 2019-12-25 | 2019-12-25 | Green method for preparing butanol and octanol by hydrogenation catalyst |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201911354916.6A CN111018667B (en) | 2019-12-25 | 2019-12-25 | Green method for preparing butanol and octanol by hydrogenation catalyst |
Publications (2)
Publication Number | Publication Date |
---|---|
CN111018667A true CN111018667A (en) | 2020-04-17 |
CN111018667B CN111018667B (en) | 2022-07-12 |
Family
ID=70213100
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201911354916.6A Active CN111018667B (en) | 2019-12-25 | 2019-12-25 | Green method for preparing butanol and octanol by hydrogenation catalyst |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN111018667B (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114835543A (en) * | 2022-03-17 | 2022-08-02 | 北京安胜瑞力科技有限公司 | Long-chain olefin synthesis system and synthesis process for synthesizing long-chain olefin by applying same |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
RO100615A2 (en) * | 1988-02-29 | 1991-11-11 | Institutul De Cercetari Inginerie Tehnologica Si Proiectare Pentru Rafinarii,Ploiesti, Judetul Prahova; Ro | OBTAINING PROCESS FOR A CATALYST FOR n-PARAFFINES ISOMERISATION |
CN101664682A (en) * | 2008-09-05 | 2010-03-10 | 中国石油化工股份有限公司 | Non-noble metal supported selective hydrogenation catalyst and preparation method and application thereof |
CN101973846A (en) * | 2010-11-03 | 2011-02-16 | 淄博诺奥化工有限公司 | Method for producing mixed butanol and coarse octanol by using waste liquid discharged from octanol device as raw material |
CN106187699A (en) * | 2015-04-29 | 2016-12-07 | 中国石油化工股份有限公司 | The separation and refining method of butanol and octanol waste liquid front-end hydrogenation |
-
2019
- 2019-12-25 CN CN201911354916.6A patent/CN111018667B/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
RO100615A2 (en) * | 1988-02-29 | 1991-11-11 | Institutul De Cercetari Inginerie Tehnologica Si Proiectare Pentru Rafinarii,Ploiesti, Judetul Prahova; Ro | OBTAINING PROCESS FOR A CATALYST FOR n-PARAFFINES ISOMERISATION |
CN101664682A (en) * | 2008-09-05 | 2010-03-10 | 中国石油化工股份有限公司 | Non-noble metal supported selective hydrogenation catalyst and preparation method and application thereof |
CN101973846A (en) * | 2010-11-03 | 2011-02-16 | 淄博诺奥化工有限公司 | Method for producing mixed butanol and coarse octanol by using waste liquid discharged from octanol device as raw material |
CN106187699A (en) * | 2015-04-29 | 2016-12-07 | 中国石油化工股份有限公司 | The separation and refining method of butanol and octanol waste liquid front-end hydrogenation |
Non-Patent Citations (1)
Title |
---|
杨霞: "辛醇液相加氢精制催化剂的研究", 《中国优秀博硕士学位论文全文数据库 (硕士) 工程科技Ⅰ辑》 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114835543A (en) * | 2022-03-17 | 2022-08-02 | 北京安胜瑞力科技有限公司 | Long-chain olefin synthesis system and synthesis process for synthesizing long-chain olefin by applying same |
CN114835543B (en) * | 2022-03-17 | 2024-03-22 | 北京安胜瑞力科技有限公司 | Long-chain olefin synthesis system and synthesis process for synthesizing long-chain olefin by using same |
Also Published As
Publication number | Publication date |
---|---|
CN111018667B (en) | 2022-07-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN104355975B (en) | A kind of method of acetone two step synthesis methyl iso-butyl ketone (MIBK) | |
CN109096062A (en) | Method for purifying polymethoxy dimethyl ether | |
CN112409178A (en) | Method for preparing methyl methacrylate by taking methyl acetate as raw material | |
CN111018667B (en) | Green method for preparing butanol and octanol by hydrogenation catalyst | |
CN104151138A (en) | Process for producing alcohol type high-carbon organic solvent by using n-butanol and n-octanol residual liquid | |
CN105566063A (en) | Ethanol preparation method | |
CN106187693B (en) | The cracking of butanol and octanol waste liquid collection and the separation method for adding hydrogen | |
CN108947774A (en) | A kind of method and device of separating isopropanol | |
CN103159591A (en) | Technique of synthesizing ethanol with acetic acid | |
CN103804116A (en) | Method for preparing polymer-grade isobutylene through cracking of methyl tert-butyl ether | |
CN103864587B (en) | Method for synthesizing 2-ethyl-2-hexenal | |
CN101830774A (en) | Method for preparing C2-4 dihydric alcohol and polyalcohol from starch raw materials | |
CN113443960B (en) | Preparation method of 1, 4-butanediol | |
CN110981693B (en) | Green method for preparing alcohols with high-value of octane by catalytic distillation | |
CN106187698B (en) | The separation and refining method of butanol and octanol waste liquid back end hydrogenation | |
CN109534996B (en) | Process for producing butyl levulinate by taking cellulose as raw material | |
CN109096063A (en) | The method for purifying polyoxymethylene dimethyl ethers | |
CN203256179U (en) | Technological equipment for processing methylisobutylketone | |
CN112538014A (en) | Synthesis system and method for producing butyl butyrate by butyraldehyde one-step method | |
CN111411024A (en) | Method and device for producing biodiesel by micro-reaction ester exchange | |
CN106187700A (en) | The separation method of butanol and octanol waste liquid back end hydrogenation | |
CN113801080B (en) | Method for producing furfural with low energy consumption | |
CN216725835U (en) | Partition plate type methyl propionate reaction rectifying tower with coupling hydrogenation | |
CN106187680B (en) | By the refining methd of butanol and octanol waste liquid back end hydrogenation recycling butanol and octanol | |
CN106187694B (en) | Recycle the refining methd of butanol and octanol from butanol and octanol waste liquid with hydrogenation reaction by cracking |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
CB02 | Change of applicant information | ||
CB02 | Change of applicant information |
Address after: 255400 Xin Hua Road, Linzi District, Zibo, Shandong Province, No. 2727 Applicant after: Zibo Nalcohol Chemical Co.,Ltd. Address before: 255400 Xin Hua Road, Linzi District, Zibo, Shandong Province, No. 2727 Applicant before: ZIBO NALCOHOL CHEMICAL CO.,LTD. |
|
GR01 | Patent grant | ||
GR01 | Patent grant |