CN113666796A - Alkyne-containing carbon tetra-hydrogenation method - Google Patents

Alkyne-containing carbon tetra-hydrogenation method Download PDF

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CN113666796A
CN113666796A CN202010409842.8A CN202010409842A CN113666796A CN 113666796 A CN113666796 A CN 113666796A CN 202010409842 A CN202010409842 A CN 202010409842A CN 113666796 A CN113666796 A CN 113666796A
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catalyst
microemulsion
carrier
hours
alkyne
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CN113666796B (en
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谭都平
路聿轩
王书峰
边虎
张小奇
巩红光
任峰
柏介军
李平智
瞿朝霞
李艳
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Petrochina Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
    • C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
    • 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
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    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8993—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with chromium, molybdenum or tungsten
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0203—Impregnation the impregnation liquid containing organic compounds
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0205—Impregnation in several steps
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0213—Preparation of the impregnating solution
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
    • C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
    • C07C5/08—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with noble metals
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

Acetylene-containing carbon four-hydrogenation method, extracting with butadieneThen the carbon four fraction containing alkyne is used as raw material, and unsaturated alkene is saturated and hydrogenated into alkane by adopting an adiabatic fixed bed reactor. The reaction process conditions are as follows: the temperature of a reaction inlet is 20-80 ℃, the reaction pressure is 0.5-3.0 MPa, and the volume ratio of hydrogen to oil is 100-500: 1, the space velocity of the fresh materials is 0.2-2 h‑1And (3) diluting ratio of 10-40: 1. the catalyst carrier is alumina or mainly alumina and has a bimodal pore distribution structure, wherein the pore diameter of a small pore is 10-40 nm, the pore diameter of a large pore is 50-420 nm, the catalyst at least contains Pd, Mo, Ni and Cu, the mass of the catalyst is 100%, the content of Pd is 0.10-0.55 wt%, and the mass ratio of Mo to Pd is 2-12: 1, the Ni content is 0.1-6 wt%, the mass ratio of Cu to Ni is 0.1-1: 1, wherein Ni and Cu are loaded in a microemulsion mode and distributed in macropores of a carrier; mo is loaded by a solution method, and Pd is loaded by a solution method and a microemulsion method. The method solves the problem of insufficient cracking material of the ethylene device, and simultaneously reduces the comprehensive cost of ethylene.

Description

Alkyne-containing carbon tetra-hydrogenation method
Technical Field
The invention relates to a hydrogenation method for alkyne-containing four-component hydrocarbon, in particular to a method for hydrogenating residual high alkyne-containing four-component tail gas into alkane after butadiene extraction.
Background
At present, butadiene, isobutene and a small amount of n-butene in the four-carbon fraction are partially utilized to prepare chemical products, and 60-70% of the four-carbon fraction is burnt out as fuel with low added value. Therefore, the four carbon components after the butadiene and the isobutene are extracted are hydrogenated into the tetrakane hydrocarbon which is used as a raw material for preparing the ethylene by cracking, so that the problem of insufficient cracking materials of an ethylene device is solved, the comprehensive cost of the ethylene is reduced, and the tetrakane hydrocarbon has a certain effect of improving the overall economic benefit of a petrochemical device.
ZL201110267118.7 discloses a saturated hydrogenation method of four carbon and five carbon fractions in petroleum hydrocarbon cracking, the used catalyst is a nickel-based hydrogenation catalyst, and the method is characterized in that the hydrogenation process conditions are as follows: the inlet temperature of the reactor is 30-50 ℃, the reaction pressure is 1.0-4.0 MPa, and the liquid volume space velocity is 1.0-5.0 h-1The volume ratio of hydrogen to oil is 100-400; the nickel-based hydrogenation catalyst is prepared by loading active components and auxiliary components on a carrier, and comprises a main active component Ni, auxiliary active components Mg, Mo, Sn, X1 and a carrier X2.
ZL201110401902.2 relates to a process for the total hydrogenation of unsaturated hydrocarbon fractions; butadiene unit extracting residual carbon four material and H2Entering two hydrogenation reactors A connected in series, wherein the inlet temperature of the hydrogenation reactors is 30-45 ℃, the reaction pressure is 1.0-2.5 MPa, and the liquid hourly space velocity is 2.0-5.0 h-1(ii) a The catalyst in the hydrogenation reactor is an alumina-loaded palladium-based catalyst or a copper-based catalyst, so as to obtain a carbon four-material A; carbon four materials A and H2Mixing the mixture and entering two hydrogenation reactors B connected in series, wherein the reaction temperature is 110-160 ℃, the pressure is 3.0-5.0 MPa, and the feeding volume space velocity is 3.0-6.0 h-1(ii) a The catalyst in the reactor is an alumina-loaded high-nickel-base catalyst to obtain a carbon four-material B with the olefin content of less than 2%; the product can be used as the carbon four material of ethylene cracking material.
ZL201210137002.6 relates to a method for improving the utilization value of mixed C4; the cracking C4 is selectively hydrogenated to remove alkyne, so that vinylacetylene and 1-butyne in the cracking C are hydrogenated to generate 1, 3-butadiene and 1-butene, and the alkyne content in the hydrogenated product is less than 15 x 10-9(ii) a The obtained material is subjected to extractive distillation to separate 1, 3-butadiene from other C-C fractions, and the residual C-C stream is mixed with C-C of a refinery and then subjected to hydroisomerization reaction to enable 1-butene in the mixed C-C to be iso-buteneThe product is composed into 2-butylene, and an isobutene product is obtained by separating an isomerization product; the residual C-IV material flow enters into a disproportionation reaction, so that 2-butylene in the residual C-IV material flow and ethylene are subjected to a disproportionation reaction to produce propylene, unreacted ethylene after separation and the residual C-IV material flow enter into a full hydrogenation reaction, and the product can be used as a high-quality ethylene cracking material.
CN109485535A discloses a full hydrogenation method of unsaturated hydrocarbons in four carbon cuts, which is carried out in a reaction equipment comprising a first-stage hydrogenation reactor (I), a second-stage hydrogenation reactor (II) and a vapor-liquid separation tank (III), and the method comprises: and (2) enabling a first carbon four-fraction raw material flow and part of liquid phase materials from the vapor-liquid separation tank (III) to enter the first-stage hydrogenation reactor (I) to perform a first full hydrogenation reaction to obtain a first hydrogenated carbon four-fraction, enabling a second carbon four-fraction raw material flow and the first hydrogenated carbon four-fraction to enter the second-stage hydrogenation reactor (II) to perform a second full hydrogenation reaction to obtain a second hydrogenated carbon four-fraction, enabling the second hydrogenated carbon four-fraction to enter the vapor-liquid separation tank (III) to perform vapor-liquid separation, returning one part of the separated liquid phase materials to the first-stage hydrogenation reactor (I), and enabling the other part of the separated liquid phase materials to be target carbon four-fraction products.
ZL201080018711.1 discloses a hydroconversion multi-metal catalyst and a preparation method thereof, the catalyst is prepared by a coprecipitation method, VIII group, IIB group, VIB group, IIA group, IVA group and other metals are added, and organic matters are also added as a coordination agent, and titanium dioxide, sodium silicate, potassium silicate, silica gel, silica sol, silica gel, hydronium-or ammonium-stabilized silica sol, sodium aluminate, potassium aluminate, aluminum sulfate, aluminum nitrate, magnesium aluminosilicate clay, magnesium metal, magnesium hydroxide, magnesium halide, magnesium sulfate, magnesium nitrate, zirconium oxide, cationic clay, anionic clay, zinc oxide, zinc sulfide, tetraethyl orthosilicate, silicic acid, niobium oxide, titanium oxide and combinations thereof are used as diluents. The catalyst is a bulk catalyst, namely a non-supported catalyst, the catalyst does not have a catalyst carrier contained in a conventional catalyst, and a supported metal is not impregnated or deposited, wherein a diluent mainly plays a role in volume dilution, and the activity of the catalyst is properly reduced; and also serves to control or adjust the mesopore porosity of the catalyst precursor.
ZL200810222182.1 discloses a selective hydrogenation catalyst and a preparation method thereof, the catalyst takes alumina as a carrier, and comprises an active component palladium, an auxiliary agent copper, an auxiliary agent X1 and an auxiliary agent X2, and the catalyst accounts for 100 percent of the total weight of the catalyst: 0.1-0.5% of palladium, 0.1-6% of copper, 10.5-15% of X, 20.5-5% of X, 0-2% of one or more auxiliary metal selected from cobalt, nickel, molybdenum, tungsten, lanthanum, silver, cerium, samarium and neodymium; wherein X1 is selected from IVA element, X2 is selected from alkali metal, alkaline earth metal or mixture thereof. The catalyst is suitable for selective hydrogenation acetylene removal of acetylene hydrocarbon residual materials after butadiene extraction, but is only suitable for processing carbon four materials with high acetylene hydrocarbon content and low butadiene content.
The hydrogenation catalyst provided by ZL200810223451.6 takes Pd and Ag bimetal as active components, and has bimodal pore distribution, wherein the radius of a small pore part can be 2-50 nm, the radius of a large pore part can be 100-420 nm, the Pd content is 0.02-0.1%, and the ratio of Ag: pd 10-1/1, the catalyst may further contain alkali metal and/or alkaline earth metal in an amount of 0-5.0%, and the specific surface area of the catalyst is 30-90 m2The pore volume is 0.3 to 0.6 mL/g. Has good hydrogenation activity, good selectivity and large ethylene increment.
Patent ZL201310114079.6 discloses a preparation method of a high-coking resistance selective hydrogenation catalyst, wherein a catalyst carrier is mainly alumina, has a bimodal pore distribution structure and contains double active components Pd and Ni, the active components Pd are loaded by adopting an aqueous solution impregnation method, and the Ni is loaded by adopting a W/O microemulsion impregnation method. After the method is adopted, Pd and Ni are positioned in pore channels with different pore diameters, green oil generated by reaction is saturated and hydrogenated in a large pore, and the coking amount of the catalyst is reduced. However, the reduction temperature of Ni is often about 500 ℃, and the reduced Pd atoms are easy to gather at the temperature, so that the activity of the catalyst is greatly reduced.
Disclosure of Invention
The invention aims to provide a hydrogenation method for alkyne-containing C-tetrads, and particularly provides a hydrogenation method for acetylene-containing C-tetrads after butadiene extraction, which is used for treating butane, butylene, butadiene, vinyl acetylene, butyne and other C-tetrads, performing saturated hydrogenation reaction on the butane-containing C-tetrads to serve as ethylene cracking materials, so that the problem of insufficient cracking materials of an ethylene device is solved, and the comprehensive cost of ethylene is reduced.
The invention relates to an alkyne hydrogenation method, which comprises a material to be hydrogenated and H2And (4) entering an adiabatic bed reactor for selective hydrogenation, wherein the reactor is filled with a catalyst. The reaction process conditions are as follows: the temperature of a reaction inlet is 20-80 ℃, the reaction pressure is 0.5-3.0 MPa, and the volume ratio of hydrogen to oil is 100-500: 1, the space velocity of the fresh materials is 0.2-2 h-1And (3) diluting ratio of 10-40: 1, cooling the reaction product, and then separating the reaction product in a gas-liquid separation tank.
In the method disclosed by the invention, the adiabatic reactor is a trickle bed adiabatic reactor or a bubbling bed adiabatic reactor. The present invention preferably uses a bubbling bed adiabatic reactor, preferably a single or multi-stage adiabatic bubbling bed reactor. For a single-stage adiabatic bubbling bed reactor, the airspeed of the fresh materials is preferably 0.5-1.0 h-1. The multistage adiabatic bubbling bed reactor is a reactor containing two or more stages, and when the multistage adiabatic bubbling bed reactor is adopted, the airspeed of the fresh materials is preferably 1.0-1.5 h-1. According to the method disclosed by the invention, different reaction conditions can be selected in the adiabatic reactor according to different raw materials, and the reaction is a liquid phase reaction, so that the raw materials are in a liquid state by selecting the temperature and the pressure, and the temperature cannot be too high so as to prevent the polymerization of olefin and alkyne, therefore, the temperature of a reaction inlet is preferably 30-55 ℃, the reaction pressure is preferably 1.0-2.0 MPa, and the volume ratio of hydrogen to oil is preferably 200-400: 1, the space velocity of the fresh materials is preferably 0.5-1.5 h-1The dilution ratio is preferably 20-30: 1, cooling the reaction product, and then separating the reaction product in a gas-liquid separation tank.
The material to be hydrogenated is a mixture of carbon four fraction containing alkyne and diluent. Preferably, the alkyne-containing carbon four cut is diluted with a diluent to an olefin content of less than 10 wt%; the most commonly used diluents are the self-hydrogenation product, raffinate carbon four and pyrolysis carbon four.
A selective hydrogenation catalyst is filled in the fixed bed reactor, a carrier of the selective hydrogenation catalyst is alumina or mainly alumina, the selective hydrogenation catalyst has a bimodal pore distribution structure, wherein the pore diameter of a small pore is 10-40 nm, the pore diameter of a large pore is 50-420 nm, the catalyst at least contains Pd, Mo, Ni and Cu, the content of Pd is 0.10-0.55 wt%, preferably 0.2-0.45 wt%, the mass ratio of Mo to Pd is 2-12: 1, preferably 3-6: 1, Ni content is 0.1-6 wt%, preferably 0.5-3.5%, and mass ratio of Cu to Ni is 0.1-1: 1, wherein Ni and Cu are loaded in a micro-emulsion manner and distributed in macropores of a carrier; mo is loaded by a solution method, and Pd is loaded by a solution method and a microemulsion method.
The inventor finds that: the alkyne-containing carbon four-saturated hydrogenation reaction mainly occurs in a main active center consisting of Pd and Mo, and macromolecules such as green oil and the like generated in the reaction can more easily enter macropores of the catalyst. In the macropores of the catalyst, Ni/Cu components are loaded, wherein Ni has a saturated hydrogenation function, and relatively large molecules such as green oil and the like can perform a saturated hydrogenation reaction in an active center consisting of Ni/Cu. Because the hydrogenation saturation is more complete, the polymerization reaction of relatively large molecules such as green oil and the like can not occur any more or the polymerization reaction rate is greatly reduced, the chain growth reaction is terminated or delayed, a large molecular weight fused ring compound can not be formed, and the fused ring compound is easily carried out of the reactor by materials, so the coking degree on the surface of the catalyst is greatly reduced, and the service life of the catalyst is greatly prolonged.
The method for controlling the Ni/Cu to be positioned in the catalyst macropores is to load the Ni/Cu in the form of microemulsion, wherein the grain diameter of the microemulsion is larger than the pore diameter of carrier micropores and smaller than the pore diameter of macropores. The nickel and copper metal salts are contained in the microemulsion and, due to steric resistance, are difficult to access to the smaller size pores of the support and therefore mainly to the macropores of the support.
The inventor also finds that the reduction temperature of Ni can be greatly reduced after Cu and Ni are loaded together, because the reduction temperature is generally required to reach 450 ℃ or even 500 ℃ for completely reducing NiO, and the temperature is too high for Pd to cause the aggregation of Pd, and the reduction temperature can be reduced by more than 100 ℃ to 350 ℃ compared with the reduction temperature of pure Ni after Cu is added to form a Cu/Ni specific structure. Thereby alleviating the agglomeration of Pd.
The inventor surprisingly found that if a small amount of Pd is loaded on the surface of Ni/Cu, the reduction temperature of Ni can be greatly reduced and can reach below 200 ℃ and as low as 150 ℃.
The catalyst adopted by the invention has active components Pd and Mo loaded by adopting an aqueous solution method, Ni, Cu and a small amount of Pd loaded by adopting a W/O microemulsion impregnation method, wherein the mass fraction of the Pd is 1/100-1/200 of the mass fraction of the Ni and the Cu. It is recommended that the impregnation with the solution of Pd is carried out by a supersaturated impregnation method. That is, most of Pd is loaded by a solution method, a small part of Pd is loaded in a microemulsion mode, and the particle size of the microemulsion is controlled to be more than 50nm and less than 420nm when the Pd is loaded in the microemulsion mode, so that the part of Pd is distributed in macropores of the carrier.
The catalyst Pd is mainly present in small pores of the catalyst, Ni/Cu is present in large pores of the catalyst, and a small amount of Pd is also present on the surface of the Ni/Cu in the large pores. Therefore, in the preparation process of the catalyst, after Ni and Cu are loaded, a small amount of Pd is loaded in macropores by a microemulsion method, and the amount of the loaded Pd is 1/100-1/200 of the content of Ni and Cu.
The carrier adopted by the invention is alumina or mainly alumina and Al2O3The crystal form is preferably alpha, theta or a mixed crystal form thereof. The alumina content in the catalyst carrier is preferably above 80%, and the carrier may also contain other metal oxides such as magnesia, titania, etc.
The invention is not particularly limited to the process of loading Ni, Cu and Pd in a microemulsion mode, and Ni, Cu and Pd can be distributed in the macropores of the carrier as long as the particle size of the microemulsion which is larger than the pore size of the small pores and smaller than the pore size of the large pores can be formed.
The invention also proposes a method, wherein the microemulsion mode loading process comprises the following steps: dissolving precursor salt in water, adding oil phase, surfactant and cosurfactant, and stirring to form microemulsion, wherein the oil phase is alkane or cycloalkane, the surfactant is ionic surfactant and/or nonionic surfactant, and the cosurfactant is organic alcohol.
The kind and addition amount of the oil phase, the surfactant and the co-surfactant are not particularly limited in the present invention, and can be determined according to the pore structures of the precursor salt and the carrier.
The oil phase recommended by the invention is saturated alkane or cycloalkane, preferably C6-C8 saturated alkane or cycloalkane, preferably cyclohexane and n-hexane; the surfactant is an ionic surfactant and/or a nonionic surfactant, preferably a nonionic surfactant, more preferably polyethylene glycol octyl phenyl ether (Triton X-100) or Cetyl Trimethyl Ammonium Bromide (CTAB); the cosurfactant is organic alcohol, preferably C4-C6 alcohol, more preferably n-butanol and/or n-pentanol.
In the microemulsion, the weight ratio of the water phase to the oil phase is preferably 2-3, the weight ratio of the surfactant to the oil phase is preferably 0.15-0.6, and the weight ratio of the surfactant to the co-surfactant is preferably 1-1.2.
The step of loading the microemulsion with Pd is preferably after the step of loading the microemulsion with Ni and Cu.
The invention also provides a more specific catalyst, and a preparation method of the catalyst comprises the following steps:
(1) dissolving a precursor salt of Pd in water, adjusting the pH value to 1.8-2.8, adding a carrier into a Pd salt solution, soaking and adsorbing for 0.5-4 h, drying for 1-6 h at 80-150 ℃, and roasting for 2-6 h at 350-550 ℃ to obtain a semi-finished catalyst A.
(2) The Mo is loaded by a saturated dipping method, namely the prepared Mo salt solution is 80-120% of the saturated water absorption of the carrier. After Mo is loaded on the semi-finished catalyst A, drying the semi-finished catalyst A for 1 to 6 hours at a temperature of between 80 and 150 ℃, and roasting the semi-finished catalyst A for 2 to 6 hours at a temperature of between 350 and 550 ℃. Obtaining a semi-finished product catalyst B.
(3) Dissolving precursor salts of Ni and Cu in water, adding an oil phase, a surfactant and a cosurfactant, fully stirring to form a microemulsion, and controlling the particle size of the microemulsion to be larger than the pore diameter of a small hole of a carrier and smaller than the pore diameter of a large hole of the carrier. And adding the semi-finished catalyst B into the prepared microemulsion, soaking for 0.5-4 hours, and filtering out residual liquid. Drying at 60-120 ℃ for 1-6 hours, and roasting at 300-600 ℃ for 2-8 hours. Obtaining a semi-finished product catalyst C.
(4) Dissolving Pd precursor salt in water, adding oil phase, surfactant and cosurfactant, stirring to form microemulsion, and controlling the particle size of the microemulsion to be larger than the pore size of the carrier pores and smaller than the pore size of the carrier macropores. And adding the semi-finished catalyst C into the prepared microemulsion, soaking for 0.5-4 hours, and filtering out residual liquid. Drying at 60-120 ℃ for 1-6 hours, and roasting at 300-600 ℃ for 2-8 hours. The desired catalyst is obtained.
In the above preparation steps, step (1) precedes step (2), step (3) precedes step (4), and step (3) may precede step (1).
The carrier in the step (1) can be spherical, cylindrical, clover-shaped and the like.
The precursor salts of Ni, Cu, Mo and Pd in the above steps are soluble salts, and can be nitrates, chlorides or other soluble salts thereof.
According to the hydrogenation method, before the catalyst is put into the hydrogenation reaction, the catalyst is reduced at the reduction temperature of 150-200 ℃.
The catalyst had the following characteristics: at the beginning of the hydrogenation reaction, because the hydrogenation activity of palladium is high and the palladium is mainly distributed in small holes, the saturated hydrogenation reaction containing alkyne-carbon four mainly occurs in the small holes and a small amount occurs in the large holes. With the prolonging of the operation time of the catalyst, a part of by-products with larger molecular weight are generated on the surface of the catalyst, and the substances enter large pores more due to larger molecular size and have longer retention time, and can generate saturated hydrogenation reaction under the action of the nickel catalyst to generate saturated hydrocarbon or aromatic hydrocarbon without isolated double bonds, and do not generate substances with larger molecular weight any more.
The inventors have found that the initial activity of the catalyst prepared by this method is significantly improved compared to a bimodal pore distribution catalyst without palladium.
The inventor also finds that the coking resistance of the catalyst is obviously improved after the hydrogenation method is used.
The specific implementation mode is as follows:
the catalyst of the invention is characterized by the following methods in the preparation process: analyzing the microemulsion particle size distribution on a dynamic light scattering particle size analyzer; measuring the small holes and the specific surface area of the carrier by adopting a physical adsorption instrument; measuring the macroporous structure of the carrier by using a mercury porosimeter; the contents of Pd, Mo, Ni and Cu in the catalyst were determined on an atomic absorption spectrometer.
Example 1
Catalyst carrier: a commercially available clover bar-shaped alumina carrier with double-peak hole distribution is adopted, and the diameter is 2-3 mm. Roasting at 1040 ℃, wherein the bimodal pore size distribution ranges from 10 nm to 32nm and from 90 nm to 350nm, the water absorption rate is 62%, and the specific surface area is 59m2(ii) in terms of/g. 100g of the carrier was weighed.
Preparing a catalyst:
(1) weighing nickel nitrate and copper chloride, dissolving in 58mL deionized water, adding cyclohexane 26.13g, Triton X-1008.11 g and n-butanol 7.53g, stirring thoroughly to form microemulsion, soaking 100g of the carrier calcined at high temperature in the prepared microemulsion, shaking for 40min, filtering to remove residual liquid, and washing with deionized water. Drying at 80 deg.C for 6 hr, and calcining at 400 deg.C for 4 hr. Referred to as semi-finished catalyst a.
(2) Preparing palladium chloride into an active component impregnation liquid, adjusting the pH value to 2.4, then impregnating the semi-finished catalyst A into the prepared palladium active component solution, drying for 6 hours at 80 ℃ after 30min of impregnation, and roasting for 4 hours at 500 ℃. Obtaining a semi-finished product catalyst B.
(3) Weighing ammonium molybdate, dissolving the ammonium molybdate in deionized water, soaking the semi-finished catalyst B prepared in the step (2) in the prepared solution, shaking, drying at 120 ℃ for 3 hours after the solution is completely absorbed, and roasting at 500 ℃ for 6 hours to obtain a semi-finished catalyst C.
(4) Preparing active component impregnation liquid from palladium chloride, 26.13g of cyclohexane, 26.13g of Triton X-1008.11 g of n-butanol and 7.53g of n-butanol, fully stirring to form microemulsion, placing the semi-finished catalyst C in the prepared microemulsion, shaking for 30min, filtering residual liquid, and washing with deionized water. Drying at 80 deg.C for 6 hr, and calcining at 400 deg.C for 6 hr to obtain the desired catalyst.
The particle size of the microemulsion prepared was 153nm as determined by dynamic light scattering.
And (3) catalyst reduction:
before use, the mixture is placed in a fixed bed reaction device and is mixed with N2:H2Reducing the mixed gas at the temperature of 190 ℃ for 10h under the condition of 1: 1.
Comparative example 1
The same support as in example 1 was used, and the catalyst preparation conditions were the same as in example 1 except that Cu was not supported.
Preparing a catalyst:
(1) weighing nickel nitrate, dissolving in 58mL of deionized water, adding 26.13g of cyclohexane, 26.13g of Triton X-1008.11 g of n-butanol and 7.13g of n-butanol, fully stirring to form a microemulsion, dipping 100g of the weighed carrier calcined at high temperature into the prepared microemulsion, shaking for 40min, filtering out residual liquid, and washing with deionized water. Dried at 80 ℃ for 6 hours and calcined at 400 ℃ for 4 hours, referred to as semi-finished catalyst A1.
(2) Preparing palladium chloride into an active component impregnation liquid, adjusting the pH value to 2.4, then impregnating the semi-finished catalyst A1 into the prepared palladium active component solution, drying for 6 hours at 80 ℃ after impregnating for 30 minutes, and roasting for 4 hours at 500 ℃ to obtain a semi-finished catalyst B1.
(3) Weighing ammonium molybdate, dissolving the ammonium molybdate in deionized water, soaking the semi-finished catalyst B1 prepared in the step (2) in the prepared solution, shaking, drying at 120 ℃ for 3 hours after the solution is completely absorbed, and roasting at 500 ℃ for 6 hours to obtain the semi-finished catalyst C1.
(4) Preparing active component impregnation liquid from palladium chloride, 26.13g of cyclohexane, 26.13g of Triton X-1008.11 g of n-butanol and 7.53g of n-butanol, fully stirring to form microemulsion, placing the semi-finished catalyst C1 in the prepared microemulsion, shaking for 30min, filtering out residual liquid, and washing with deionized water. Drying at 80 deg.C for 6 hr, and calcining at 400 deg.C for 6 hr to obtain the desired catalyst.
The particle size of the microemulsion prepared was 153nm as determined by dynamic light scattering.
And (3) catalyst reduction:
before use, the mixture is placed in a fixed bed reaction device and is mixed with N2:H21:1 mixed gasReducing the mixture at 190 ℃ for 10 h.
Comparative example 2
The catalyst preparation process was the same as in comparative example 1 except that the catalyst reduction temperature was 350 ℃.
The implementation effect is as follows:
reaction process conditions are as follows: diluting the carbon four fraction containing alkyne with the self product and the raffinate carbon four at a dilution ratio of 30: 1. The adiabatic reactor adopts a single-section adiabatic bubbling bed, the temperature of a reaction inlet is 45 ℃, the reaction pressure is 1.5MPa, and the space velocity of fresh oil is 0.7h-1The hydrogen-oil volume ratio was 350:1, the composition of the reaction material is shown in Table 1, and the catalyst evaluation results are shown in Table 2.
TABLE 1 reaction Material composition
Figure BDA0002491247850000091
TABLE 2 evaluation results of catalysts
Figure BDA0002491247850000092
Example 2
Carrier: a commercially available spherical alumina carrier with bimodal pore distribution and a diameter of 3mm is used. After roasting at 1010 ℃, the bimodal pore size distribution ranges from 10 nm to 35nm and from 100 nm to 380nm, the water absorption rate is 65%, and the specific surface area is 57m2(ii) in terms of/g. 100g of the carrier was weighed.
Preparing a catalyst:
(1) weighing nickel chloride and copper nitrate, dissolving in 65mL deionized water, adding 22.75g of n-heptane, 3.52g of CTAB and 3.45g of n-amyl alcohol, fully stirring to form microemulsion, dipping 100g of the carrier calcined at high temperature into the prepared microemulsion, shaking for 60min, filtering out residual liquid, and washing with deionized water. Drying at 100 deg.C for 5 hr, and calcining at 500 deg.C for 4 hr to obtain semi-finished catalyst D.
(2) Preparing palladium chloride into an active component impregnation liquid, adjusting the pH value to 2.3, then impregnating the semi-finished product catalyst D into the prepared Pd active component solution, drying for 5 hours at 100 ℃ after impregnating for 60 minutes, and roasting for 6 hours at 400 ℃ to obtain a semi-finished product catalyst E.
(3) Weighing molybdenum oxide, dissolving the molybdenum oxide in an acidic aqueous solution, soaking the semi-finished catalyst E prepared in the step (2) in the prepared solution, shaking, drying for 2 hours at 140 ℃ after the solution is completely absorbed, and roasting for 4 hours at 500 ℃ to obtain a semi-finished catalyst F.
(4) Preparing active component impregnation liquid from palladium chloride, 22.75g of n-heptane, 3.52g of CTAB and 3.45g of n-amyl alcohol, fully stirring to form microemulsion, placing the semi-finished catalyst F in the prepared microemulsion, shaking for 30min, filtering residual liquid, and washing with deionized water. Drying at 100 deg.C for 5 hr, and calcining at 450 deg.C for 6 hr to obtain the desired catalyst.
The particle size of the microemulsion prepared was 92nm as determined by dynamic light scattering.
And (3) catalyst reduction:
before use, the mixture is placed in a fixed bed reaction device and is mixed with N2:H2Reducing the mixed gas at 160 ℃ for 8h, wherein the mixed gas is 1: 1.
Comparative example 3
The same support as in example 2 was used, and the catalyst preparation conditions were the same as in example 2, except that Cu was supported by a solution method.
Preparing a catalyst:
(1) weighing nickel chloride, dissolving in 65mL deionized water, adding 22.75g of n-heptane, 3.52g of CTAB and 3.45g of n-amyl alcohol, fully stirring to form a microemulsion, dipping 100g of the carrier calcined at high temperature into the prepared microemulsion, shaking for 60min, filtering out residual liquid, and washing with deionized water. Dried at 100 ℃ for 5 hours and calcined at 500 ℃ for 4 hours, referred to as semi-finished catalyst D1.
(2) Preparing palladium chloride into an active component impregnation liquid, adjusting the pH value to 2.3, then impregnating the semi-finished catalyst D1 into the prepared Pd active component solution, drying for 5 hours at 100 ℃ after impregnating for 60 minutes, and roasting for 6 hours at 400 ℃ to obtain the semi-finished catalyst E1.
(3) Weighing molybdenum oxide and copper nitrate, dissolving in an acidic aqueous solution, soaking the semi-finished catalyst E1 in the prepared solution, shaking, drying at 140 ℃ for 2 hours after the solution is completely absorbed, and roasting at 500 ℃ for 4 hours to obtain the semi-finished catalyst F1.
(4) Preparing active component impregnation liquid from palladium chloride, 22.75g of n-heptane, 3.52g of CTAB and 3.45g of n-amyl alcohol, fully stirring to form microemulsion, placing the semi-finished catalyst F1 in the prepared microemulsion, shaking for 30min, filtering residual liquid, and washing with deionized water. Drying at 100 deg.C for 5 hr, and calcining at 450 deg.C for 6 hr to obtain the desired catalyst.
The particle size of the microemulsion prepared was 92nm as determined by dynamic light scattering.
And (3) catalyst reduction:
before use, the mixture is placed in a fixed bed reaction device and is mixed with N2:H2Reducing the mixed gas at the temperature of 160 ℃ for 8h, wherein the mixed gas is 1: 1.
Comparative example 4
The catalyst was prepared under the same conditions as in comparative example 3, except that it was placed in a fixed bed reactor in a molar ratio of N before use2:H2Reducing the mixed gas at 250 ℃ for 8h under the condition of 1: 1.
The implementation effect is as follows:
reaction process conditions are as follows: diluting the carbon four fraction containing alkyne with the self product and the raffinate carbon four at a dilution ratio of 25: 1. The adiabatic reactor adopts a single-section adiabatic bubbling bed, the temperature of a reaction inlet is 40 ℃, the reaction pressure is 1.2MPa, and the space velocity of fresh oil is 0.6h-1The hydrogen-oil volume ratio was 300:1, the reaction material composition is shown in Table 3, and the catalyst evaluation results are shown in Table 4.
TABLE 3 reaction Material composition
Figure BDA0002491247850000121
TABLE 4 catalyst evaluation results
Figure BDA0002491247850000122
Example 3
Carrier: a commercially available spherical alumina carrier with bimodal pore distribution and a diameter of 4mm was used. After roasting for 4 hours at 1050 ℃, the bimodal pore size distribution ranges from 15 to 35nm and 115 to 400nm, the water absorption rate is 58 percent, and the specific surface area is 47m2(ii) in terms of/g. 100g of the carrier was weighed.
Preparing a catalyst:
(1) weighing nickel chloride and copper nitrate, dissolving in 55mL of deionized water, adding 25.4G of n-hexane, 25.25G of polyoxyethylene octylphenol ether-104.95G of polyoxyethylene octylphenol ether and 4.92G of n-hexanol, fully stirring to form a microemulsion, dipping 100G of the weighed carrier calcined at high temperature into the prepared microemulsion, shaking for 120min, filtering out residual liquid, washing with deionized water, drying at 120 ℃ for 3 hours, and calcining at 380 ℃ for 2 hours to obtain a semi-finished product catalyst G.
(2) Preparing palladium nitrate into an active component impregnation liquid, adjusting the pH value to 2.2, then impregnating the semi-finished product catalyst G into the prepared palladium active component solution, drying for 4 hours at 120 ℃ after impregnating for 90 minutes, and roasting for 4 hours at 500 ℃ to obtain a semi-finished product catalyst H.
(3) Weighing ammonium molybdate, dissolving the ammonium molybdate in deionized water, soaking the semi-finished catalyst H prepared in the step (2) in the prepared solution, shaking, drying at 150 ℃ for 2 hours after the solution is completely absorbed, and roasting at 500 ℃ for 6 hours to obtain a semi-finished catalyst I.
(4) Preparing active component impregnation liquid from palladium chloride, 25.4g of n-hexane, 25.4g of polyoxyethylene octylphenol ether-104.95 g of polyoxyethylene and 4.92g of n-hexanol, fully stirring to form a microemulsion, placing the semi-finished catalyst I in the prepared microemulsion, shaking for 30min, filtering out residual liquid, and washing with deionized water. Drying at 120 deg.C for 3 hr, and calcining at 380 deg.C for 2 hr to obtain the desired catalyst.
The particle size of the microemulsion prepared was 114nm as determined by dynamic light scattering.
And (3) catalyst reduction:
before use, the mixture is placed in a fixed bed reaction device and is reduced by pure hydrogen for 8 hours at the temperature of 150 ℃.
Comparative example 5
The same support as in example 3 was used, and the catalyst preparation conditions were the same as in example 3, except that no emulsion method was used to support Pd.
Preparing a catalyst:
(1) weighing nickel chloride and copper nitrate, dissolving in 55mL of deionized water, adding 25.4G of n-hexane, 104.95G of polyoxyethylene octylphenol ether and 4.92G of n-hexanol, fully stirring to form a microemulsion, dipping 100G of the weighed carrier calcined at high temperature into the prepared microemulsion, shaking for 120min, filtering out residual liquid, washing with deionized water, drying at 120 ℃ for 3 hours, and calcining at 380 ℃ for 2 hours to obtain a semi-finished product catalyst G1.
(2) Preparing palladium nitrate into an active component impregnation liquid, adjusting the pH value to 2.2, then impregnating a semi-finished catalyst G1 into the prepared palladium active component solution, drying for 4 hours at 120 ℃ after impregnating for 90 minutes, and roasting for 4 hours at 500 ℃ to obtain a semi-finished catalyst H1.
(3) Weighing ammonium molybdate, dissolving the ammonium molybdate in deionized water, soaking the semi-finished catalyst H1 prepared in the step (2) in the prepared solution, shaking, drying at 150 ℃ for 2 hours after the solution is completely absorbed, and roasting at 500 ℃ for 5 hours to obtain the required catalyst.
The particle size of the microemulsion prepared was 114nm as determined by dynamic light scattering.
And (3) catalyst reduction:
before use, the mixture is placed in a fixed bed reaction device and is reduced by pure hydrogen for 8 hours at the temperature of 150 ℃.
Comparative example 6
The catalyst preparation conditions were the same as in comparative example 5 except that the catalyst reduction temperature was 300 ℃.
The implementation effect is as follows:
reaction process conditions are as follows: diluting the carbon four fraction containing alkyne with the self product and the raffinate carbon four at a dilution ratio of 30: 1. The adiabatic reactor adopts a single-section adiabatic bubbling bed, the temperature of a reaction inlet is 48 ℃, the reaction pressure is 1.8MPa, and the space velocity of fresh oil is 0.8h-1The hydrogen-oil volume ratio was 320:1, the reaction material composition is shown in Table 5, and the catalyst evaluation results are shown in Table 6.
TABLE 5 reaction Material composition
Figure BDA0002491247850000141
TABLE 6 evaluation results of catalysts
Figure BDA0002491247850000142
Example 4
Carrier: a commercially available spherical alumina-titania carrier with bimodal pore distribution is adopted, the content of magnesia is 3%, and the diameter is 3 mm. After roasting for 4 hours at 1000 ℃, the bimodal pore size distribution ranges from 10 nm to 30nm and from 75 nm to 260nm, the water absorption rate is 71 percent, and the specific surface area is 68m2(ii) in terms of/g. 100g of the carrier was weighed.
Preparing a catalyst:
(1) weighing nickel nitrate and copper chloride, dissolving in 65mL deionized water, adding 24.17g of cyclohexane, 6.04g of CTAB and 5.05g of n-amyl alcohol, fully stirring to form a microemulsion, dipping 100g of the weighed carrier calcined at high temperature into the prepared microemulsion, shaking for 90min, filtering out residual liquid, washing with deionized water, drying at 80 ℃ for 4 hours, and calcining at 600 ℃ for 2 hours to obtain a semi-finished product catalyst J.
(2) Preparing active component impregnation liquid from 24.17g of palladium chloride, 24.17g of cyclohexane, 6.04g of CTAB and 5.05g of n-amyl alcohol, fully stirring to form microemulsion, placing the semi-finished catalyst J in the prepared microemulsion, shaking for 30min, filtering residual liquid, and washing with deionized water. Drying at 80 deg.C for 4 hr, and calcining at 600 deg.C for 2 hr to obtain semi-finished catalyst K.
(3) Preparing palladium nitrate into an active component impregnation liquid, adjusting the pH value to 2.5, then impregnating the semi-finished product catalyst K into the prepared palladium active component solution, drying for 6 hours at 110 ℃ after impregnating for 80 minutes, and roasting for 4 hours at 550 ℃ to obtain a semi-finished product catalyst L.
(4) Weighing ammonium molybdate, dissolving the ammonium molybdate in deionized water, soaking the semi-finished catalyst L in the prepared solution, shaking, drying at 100 ℃ for 5 hours after the solution is completely absorbed, and roasting at 450 ℃ for 6 hours to obtain the required catalyst.
The particle size of the microemulsion prepared was 131nm as determined by dynamic light scattering.
And (3) catalyst reduction:
before use, the mixture is placed in a fixed bed reaction device and is mixed with N2:H21:1 at 200 ℃ for 8 h.
Comparative example 7
The support and the preparation conditions were the same as in example 4, except that no Ni was present in the comparative example.
Preparing a catalyst:
(1) weighing copper chloride, dissolving in 65mL of deionized water, adding 24.17g of cyclohexane, 6.04g of CTAB and 5.05g of n-amyl alcohol, fully stirring to form a microemulsion, soaking 100g of the weighed carrier calcined at high temperature into the prepared microemulsion, shaking for 90min, filtering out residual liquid, washing with deionized water, drying at 80 ℃ for 4 hours, and calcining at 600 ℃ for 2 hours, thus obtaining the semi-finished catalyst J1.
(2) Preparing active component impregnation liquid from 24.17g of palladium chloride, 24.17g of cyclohexane, 6.04g of CTAB and 5.05g of n-amyl alcohol, fully stirring to form microemulsion, placing the semi-finished catalyst J in the prepared microemulsion, shaking for 30min, filtering residual liquid, and washing with deionized water. Dried at 80 ℃ for 4 hours and calcined at 600 ℃ for 2 hours, called semi-finished catalyst K1.
(3) Preparing palladium nitrate into an active component impregnation liquid, adjusting the pH value to 2.5, then impregnating the semi-finished catalyst K into the prepared palladium active component solution, drying for 6 hours at 110 ℃ after impregnating for 80 minutes, and roasting for 4 hours at 550 ℃ to obtain a semi-finished catalyst L1.
(4) Weighing ammonium molybdate, dissolving the ammonium molybdate in deionized water, soaking the semi-finished catalyst L in the prepared solution, shaking, drying at 100 ℃ for 5 hours after the solution is completely absorbed, and roasting at 450 ℃ for 6 hours to obtain the required catalyst.
The particle size of the microemulsion prepared was 131nm as determined by dynamic light scattering.
And (3) catalyst reduction:
before use, the mixture is placed in a fixed bed reaction device and is mixed with N2:H21:1 at 200 ℃ for 8 h.
The implementation effect is as follows:
reaction process conditions are as follows: diluting the carbon four fraction containing alkyne with the self product and the raffinate carbon four at a dilution ratio of 23: 1. The adiabatic reactor adopts a single-section adiabatic bubbling bed, the temperature of a reaction inlet is 40 ℃, the reaction pressure is 2.0MPa, and the space velocity of fresh oil is 0.5h-1The hydrogen-oil volume ratio was 300:1, the reaction material composition is shown in Table 7, and the catalyst evaluation results are shown in Table 8.
TABLE 7 reaction Mass composition
Figure BDA0002491247850000161
TABLE 8 evaluation results of catalysts
Figure BDA0002491247850000162
Example 5
Carrier: a commercially available spherical alumina-magnesia carrier with bimodal pore distribution is adopted, the magnesia content is 2.5 percent, and the diameter is 3 mm. After roasting for 4 hours at 980 ℃, the bimodal pore size distribution ranges from 15 to 35nm and 80 to 320nm, the water absorption rate is 66 percent, and the specific surface area is 65m2(ii) in terms of/g. 100g of the carrier was weighed.
Preparing a catalyst:
(1) preparing palladium chloride into active component impregnation liquid, adjusting the pH value to 2.4, impregnating 100g of the weighed carrier calcined at high temperature into the active component impregnation liquid, drying for 6 hours at 90 ℃ after 30min of impregnation, and calcining for 4 hours at 500 ℃ to obtain a semi-finished product catalyst N.
(2) Weighing molybdenum oxide, dissolving the molybdenum oxide in an acidic aqueous solution, soaking the prepared semi-finished catalyst N in the prepared solution, shaking, drying at 120 ℃ for 3 hours after the solution is completely absorbed, and roasting at 500 ℃ for 6 hours to obtain a semi-finished catalyst O.
(3) Weighing nickel nitrate and copper chloride, dissolving in 60mL of deionized water, adding 23.54g of n-hexane, 23.54g of Triton X-1007.81 g of n-hexanol and 7.46g of n-hexanol, fully stirring to form a microemulsion, dipping a semi-finished product catalyst O into the prepared microemulsion, shaking for 70min, filtering out residual liquid, washing with deionized water, drying at 80 ℃ for 6 hours, and roasting at 600 ℃ for 2 hours to obtain a semi-finished product catalyst P.
(4) Preparing active component impregnation liquid from palladium chloride, 23.54g of n-hexane, 23.54g of Triton X-1007.81 g of n-hexanol and 7.46g of n-hexanol, fully stirring to form microemulsion, placing the semi-finished catalyst P in the prepared microemulsion, shaking for 100min, filtering residual liquid, and washing with deionized water. Drying at 100 deg.C for 6 hr, and calcining at 450 deg.C for 6 hr to obtain the desired catalyst.
The particle size of the microemulsion prepared was 146nm as determined by dynamic light scattering.
And (3) catalyst reduction:
before use, the mixture is placed in a fixed bed reaction device and is mixed with N2:H2Reducing the mixed gas at 180 ℃ for 8h under the condition of 1: 1.
Comparative example 8
The catalyst preparation conditions were the same as in example 5, except that the preparation steps (3) and (4) were reversed in order.
The implementation effect is as follows:
reaction process conditions are as follows: diluting the carbon four fraction containing alkyne with raffinate carbon four at a dilution ratio of 35: 1. The adiabatic reactor adopts a single-section adiabatic bubbling bed, the temperature of a reaction inlet is 40 ℃, the reaction pressure is 1.5MPa, and the space velocity of fresh oil is 0.6h-1The hydrogen-oil volume ratio was 400:1, the composition of the reaction material is shown in Table 9, and the catalyst evaluation results are shown in Table 10.
TABLE 9 reaction Mass composition
Figure BDA0002491247850000181
TABLE 10 evaluation results of catalysts
Figure BDA0002491247850000182
Example 6
Carrier: using a commercially available spherical alumina-magnesia carrier with bimodal pore distribution of oxygenThe magnesium oxide content is 5%, and the diameter is 3 mm. After roasting for 4 hours at 1030 ℃, the bimodal pore size distribution ranges from 17 nm to 39nm and 130 nm to 400nm, the water absorption rate is 58 percent, and the specific surface area is 45m2(ii) in terms of/g. 100g of the carrier was weighed.
Preparing a catalyst:
(1) weighing nickel nitrate and copper chloride, dissolving in 53mL of deionized water, adding 20.24g of cyclohexane, 5.22g of polyoxyethylene octylphenol ether-10 and 5.1g of n-hexanol, fully stirring to form a microemulsion, soaking 100g of the weighed carrier calcined at high temperature into the prepared microemulsion, shaking for 50min, filtering out residual liquid, washing with deionized water, drying at 110 ℃ for 6 hours, and calcining at 500 ℃ for 2 hours. Referred to as semi-finished catalyst Q.
(2) Preparing palladium nitrate into an active component impregnation liquid, adjusting the pH value to 2.6, then impregnating the semi-finished product catalyst Q into the prepared palladium active component solution, drying for 6 hours at 80 ℃ after 30min of impregnation, and roasting for 4 hours at 500 ℃ to obtain a semi-finished product catalyst R.
(3) Weighing ammonium molybdate, dissolving the ammonium molybdate in deionized water, soaking the semi-finished catalyst R in the prepared solution, shaking, drying at 100 ℃ for 4 hours after the solution is completely absorbed, and roasting at 600 ℃ for 2 hours to obtain the semi-finished catalyst S.
(4) Preparing active component impregnation liquid from palladium chloride, 20.24g of n-hexane, 5.22g of polyoxyethylene octylphenol ether-10 and 5.1g of cyclohexane, fully stirring to form a microemulsion, placing the semi-finished catalyst S in the prepared microemulsion, shaking for 30min, filtering out residual liquid, and washing with deionized water. Drying at 90 deg.C for 6 hr, and calcining at 420 deg.C for 6 hr to obtain the desired catalyst.
The particle size of the microemulsion prepared was 125nm as determined by dynamic light scattering.
And (3) catalyst reduction:
before use, the mixture is placed in a fixed bed reaction device and is mixed with N2:H2Reducing the mixed gas at 250 ℃ for 8h under the condition of 1: 1.
Comparative example 9
The catalyst preparation conditions were the same as in example 6, except that the catalyst reduction temperature was 400 ℃.
The implementation effect is as follows:
reaction process conditions are as follows: diluting the carbon four fraction containing alkyne with raffinate carbon four at a dilution ratio of 18: 1. The adiabatic reactor adopts a single-section adiabatic bubbling bed, the temperature of a reaction inlet is 50 ℃, the reaction pressure is 2.0MPa, and the space velocity of fresh oil is 0.5h-1The hydrogen-oil volume ratio was 300:1, the composition of the reaction material is shown in Table 11, and the catalyst evaluation results are shown in Table 12.
TABLE 11 reaction Mass composition
Figure BDA0002491247850000191
TABLE 12 evaluation results of catalysts
Figure BDA0002491247850000192
Example 7
Carrier: a commercially available spherical alumina carrier with bimodal pore distribution and a diameter of 3mm is used. After roasting for 4 hours at 1080 ℃, the bimodal pore size distribution ranges from 18 nm to 40nm and 145 nm to 420nm, the water absorption rate is 56 percent, and the specific surface area is 43m2(ii) in terms of/g. 100g of the carrier was weighed.
Preparing a catalyst:
(1) weighing nickel nitrate and copper chloride, dissolving in 50mL of deionized water, adding 18.18g of n-hexane, 8.43g of sodium bis-2-ethylhexyl sulfosuccinate and 8.12g of n-amyl alcohol, fully stirring to form microemulsion, soaking 100g of the weighed carrier calcined at high temperature into the prepared microemulsion, shaking for 110min, filtering out residual liquid, washing with deionized water, drying at 110 ℃ for 6 hours, and calcining at 500 ℃ for 2 hours to obtain the semi-finished catalyst T.
(2) Preparing palladium chloride into an active component impregnation liquid, adjusting the pH value to 2.7, then impregnating the semi-finished catalyst T into the prepared palladium active component solution, drying for 6 hours at 90 ℃ after impregnating for 50 minutes, and roasting for 4 hours at 500 ℃ to obtain a semi-finished catalyst U.
(3) Weighing ammonium molybdate, dissolving the ammonium molybdate in deionized water, soaking the semi-finished product catalyst U in the prepared solution, shaking, drying at 100 ℃ for 4 hours after the solution is completely absorbed, and roasting at 550 ℃ for 4 hours to obtain a semi-finished product catalyst V.
(4) Preparing active component impregnation liquid from palladium chloride, 18.18g of n-hexane, 8.43g of sodium bis-2-ethylhexyl sulfosuccinate and 8.12g of n-amyl alcohol, fully stirring to form microemulsion, placing the semi-finished catalyst V in the prepared microemulsion, shaking for 60min, filtering out residual liquid, and washing with deionized water. Drying at 90 deg.C for 6 hr, and calcining at 450 deg.C for 6 hr to obtain the desired catalyst.
The particle size of the microemulsion prepared was 178nm as determined by dynamic light scattering.
And (3) catalyst reduction:
before use, the mixture is placed in a fixed bed reaction device and is mixed with N2:H2Reducing the mixed gas at 150 ℃ for 8h under the condition of 1: 1.
Comparative example 10
In comparison with example 7, the catalyst preparation steps (2) and (3) were reversed.
The implementation effect is as follows:
reaction process conditions are as follows: diluting the carbon four fraction containing alkyne with raffinate carbon four at a dilution ratio of 15: 1. The adiabatic reactor adopts a two-section bed series adiabatic bubbling bed, the reaction inlet temperature is 35 ℃, the reaction pressure is 1.5MPa, and the space velocity of fresh oil is 0.8h-1The hydrogen-oil volume ratio was 300:1, the composition of the reaction material is shown in Table 13, and the catalyst evaluation results are shown in Table 14.
TABLE 13 reaction Material composition
Figure BDA0002491247850000211
TABLE 14 evaluation results of catalysts
Figure BDA0002491247850000212
Table 15 shows the content of each component of the catalysts of examples.
TABLE 15 catalyst component contents of examples
Figure BDA0002491247850000213
It can be seen from the data analysis of the examples and the comparative examples that the hydrogenation catalyst shows more excellent saturated hydrogenation activity and anti-coking performance by using the acetylene-containing carbon four-fraction as the raw material and adopting the hydrogenation method of the invention under the same process conditions, and the hydrogenation activity and the operation period of the hydrogenation catalyst can be greatly improved.
The present invention is capable of other embodiments, and various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (10)

1. A method for hydrogenating alkyne-containing carbon tetrahydride is characterized by comprising a material to be hydrogenated and H2Entering an adiabatic reactor, wherein the adiabatic reactor is loaded with a hydrogenation catalyst, and the reaction process conditions are as follows: the temperature of a reaction inlet is 20-80 ℃, the reaction pressure is 0.5-3.0 MPa, and the volume ratio of hydrogen to oil is 100-500: 1, the space velocity of the fresh materials is 0.2-2 h-1And (3) diluting ratio of 10-40: 1, cooling a reaction product, and then separating the reaction product in a gas-liquid separation tank; the carrier of the catalyst is alumina or mainly alumina, and has a bimodal pore distribution structure, wherein the pore diameter of a small pore is 10-40 nm, the pore diameter of a large pore is 50-420 nm, the catalyst at least contains Pd, Mo, Ni and Cu, the content of Pd is 0.10-0.55 wt%, preferably 0.2-0.45 wt%, the mass ratio of Mo to Pd is 2-12: 1, preferably 3-6: 1, Ni content is 0.1-6 wt%, preferably 0.5-3.5%, and mass ratio of Cu to Ni is 0.1-1: 1, wherein Ni and Cu are loaded in a micro-emulsion manner and distributed in macropores of a carrier; mo is loaded by a solution method, and Pd is loaded by a solution method and a microemulsion method.
2. The alkyne-containing tetracarbon hydrogenation process of claim 1, wherein the reaction inlet temperaturePreferably 30-55 ℃, the reaction pressure is preferably 1.0-2.0 MPa, and the volume ratio of hydrogen to oil is preferably 200-400: 1, the space velocity of the fresh materials is preferably 0.5-1.5 h-1The dilution ratio is preferably 20-30: 1.
3. the alkyne-containing carbo-tetra hydrogenation method of claim 1, wherein the material to be hydrogenated is a mixture of the alkyne-containing carbo-tetra fraction and a diluent, and the alkyne-containing carbo-tetra fraction is diluted with the diluent until the alkene content is less than 10 wt%; the diluent is self-hydrogenation product, raffinate carbon four and cracking carbon four.
4. The alkyne-containing tetracarbon hydrogenation process of claim 1 wherein the pore size of the carrier pores is 10 to 40nm, the pore size of the macropores is 50 to 420nm, and the microemulsion particle size is larger than the pore size of the carrier pores and smaller than the pore size of the macropores of the carrier.
5. The alkyne-containing tetracarbon hydrogenation process of claim 1 wherein the microemulsion mode loading process comprises: dissolving precursor salt in water, adding oil phase, surfactant and cosurfactant, and stirring to form microemulsion, wherein the oil phase is alkane or cycloalkane, the surfactant is ionic surfactant and/or nonionic surfactant, and the cosurfactant is organic alcohol.
6. The alkyne-containing tetrahydric carbon hydrogenation process according to claim 5, wherein the oil phase is a C6-C8 saturated or cyclic alkane, preferably cyclohexane, n-hexane; the surfactant is an ionic surfactant and/or a nonionic surfactant, preferably the nonionic surfactant, and more preferably polyethylene glycol octyl phenyl ether or cetyl trimethyl ammonium bromide; the cosurfactant is C4-C6 alcohol, preferably n-butanol and/or n-pentanol.
7. The alkyne-containing tetracarbon hydrogenation process of claim 5 or 6, wherein the microemulsion has a weight ratio of the aqueous phase to the oil phase of 2 to 3, a weight ratio of the surfactant to the oil phase of 0.15 to 0.6, and a weight ratio of the surfactant to the co-surfactant of 1 to 1.2.
8. The alkyne-containing tetracarbon hydrogenation process of claim 1 wherein, during the preparation of the catalyst, the order of solution loading of Pd and Ni/Cu loading is not limited; the step of loading Pd on the microemulsion is after the step of loading Ni/Cu on the microemulsion; the step of loading Mo in the solution method is after the step of loading Pd in the solution method.
9. The alkyne-containing tetracarbon hydrogenation process of claim 1 wherein the catalyst preparation process comprises the steps of:
(1) dissolving a precursor salt of Pd in water, adjusting the pH value to 1.8-2.8, adding a carrier into a Pd salt solution, soaking and adsorbing for 0.5-4 h, drying for 1-6 h at 80-150 ℃, and roasting for 2-6 h at 350-550 ℃ to obtain a semi-finished catalyst A;
(2) the Mo is loaded by a saturated dipping method, namely, the prepared Mo salt solution is 80-120% of the saturated water absorption of the carrier, the semi-finished catalyst A is dried for 1-6 hours at 80-150 ℃ after being loaded with Mo, and is roasted for 2-6 hours at 350-550 ℃ to obtain a semi-finished catalyst B;
(3) dissolving precursor salts of Ni and Cu in water, adding an oil phase, a surfactant and a cosurfactant, fully stirring to form a microemulsion, controlling the particle size of the microemulsion to be larger than the aperture of small holes of a carrier and smaller than the aperture of large holes of the carrier, adding a semi-finished catalyst B into the prepared microemulsion, soaking for 0.5-4 hours, filtering out residual liquid, drying for 1-6 hours at the temperature of 60-120 ℃, and roasting for 2-8 hours at the temperature of 300-600 ℃ to obtain a semi-finished catalyst C;
(4) dissolving Pd precursor salt in water, adding an oil phase, a surfactant and a cosurfactant, fully stirring to form a microemulsion, controlling the particle size of the microemulsion to be larger than the aperture of a small hole of a carrier and smaller than the aperture of a large hole of the carrier, adding a semi-finished catalyst C into the prepared microemulsion, soaking for 0.5-4 hours, filtering out residual liquid, drying for 1-6 hours at the temperature of 60-120 ℃, and roasting for 2-8 hours at the temperature of 300-600 ℃ to obtain the catalyst.
10. The process for the hydrogenation of a carbonium containing alkyne of claim 1, wherein the catalyst is reduced at a reduction temperature of 150 to 200 ℃ before being put into the hydrogenation reaction.
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JP2011083701A (en) * 2009-10-15 2011-04-28 Jx Nippon Oil & Energy Corp Hydrogenation catalyst exhibiting excellent anti-poison property to impurity in hydrogen source and method for producing the catalyst
CN103084169A (en) * 2011-10-28 2013-05-08 中国石油化工股份有限公司 Unsaturated hydrocarbon hydrogenation catalyst, preparation method and applications thereof
CN104096572A (en) * 2013-04-03 2014-10-15 中国石油天然气股份有限公司 Selective hydrogenation catalyst for improving coking resistance
CN108863706A (en) * 2017-05-15 2018-11-23 中国石油天然气股份有限公司 A kind of selection method of hydrotreating of the C-4-fraction containing alkynes

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1182929A (en) * 1966-12-20 1970-03-04 Nippon Oil Co Ltd Selective Hydrogenation Catalysts
JP2011083701A (en) * 2009-10-15 2011-04-28 Jx Nippon Oil & Energy Corp Hydrogenation catalyst exhibiting excellent anti-poison property to impurity in hydrogen source and method for producing the catalyst
CN103084169A (en) * 2011-10-28 2013-05-08 中国石油化工股份有限公司 Unsaturated hydrocarbon hydrogenation catalyst, preparation method and applications thereof
CN104096572A (en) * 2013-04-03 2014-10-15 中国石油天然气股份有限公司 Selective hydrogenation catalyst for improving coking resistance
CN108863706A (en) * 2017-05-15 2018-11-23 中国石油天然气股份有限公司 A kind of selection method of hydrotreating of the C-4-fraction containing alkynes

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