CN112934231B - Catalyst for hydrogenation before depropanization of carbon two fractions - Google Patents

Catalyst for hydrogenation before depropanization of carbon two fractions Download PDF

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CN112934231B
CN112934231B CN201911186465.XA CN201911186465A CN112934231B CN 112934231 B CN112934231 B CN 112934231B CN 201911186465 A CN201911186465 A CN 201911186465A CN 112934231 B CN112934231 B CN 112934231B
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catalyst
microemulsion
solution
carrier
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CN112934231A (en
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梁玉龙
车春霞
魏弢
魏铁锋
赵玉龙
苟尕莲
韩伟
温翯
柏介军
刘轶凡
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Petrochina Co Ltd
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    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/66—Pore distribution
    • B01J35/69—Pore distribution bimodal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8926—Copper and noble metals
    • 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
    • B01J37/0201—Impregnation
    • B01J37/0213—Preparation of the impregnating solution
    • 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
    • B01J37/024—Multiple impregnation or coating
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
    • C07C7/163—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation
    • C07C7/167—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation for removal of compounds containing a triple carbon-to-carbon bond
    • 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
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

The invention relates to an alkyne selective hydrogenation catalyst, in particular to a catalyst for front depropanization of carbon two fractions, wherein the carrier is alumina or mainly alumina, and has a bimodal pore distribution structure, and the specific surface area of the catalyst is 5-15 m 2 And/g. Wherein the aperture of the small hole is 50-65 nm, and the aperture of the large hole is 250-550 nm. The catalyst at least contains Pd, au, ni, cu, wherein Pd is loaded in a micro-emulsion mode and a solution mode, ni and Cu are loaded in a micro-emulsion mode, and Au is loaded in a solution mode. The catalyst has the advantages of low reduction temperature, low green oil production amount, excellent catalytic performance and coking resistance, and the mass of the catalyst is 100 percent, the content of Pd loaded in the solution is 0.035-0.065%, the weight ratio of Au to Pd loaded in the solution is 1.3-3.0, the content of Ni is 0.5-8.0%, the weight ratio of Cu to Ni is 0.1-0.9, and the content of Pd loaded in the microemulsion is 1/150-1/250 of the content of Ni+Cu.

Description

Catalyst for hydrogenation before depropanization of carbon two fractions
Technical Field
The invention relates to a high coking resistance selective hydrogenation catalyst, in particular to a high coking resistance selective hydrogenation catalyst for hydrogenation before depropanization of carbon two fractions.
Background
Ethylene is one of the most important base materials in the petrochemical industry, and as a monomer-ethylene for synthesizing various polymers, most of ethylene is produced by steam cracking of petroleum hydrocarbons (e.g., ethane, propane, butane, naphtha, light diesel, etc.). The C2 fraction containing ethylene as main component obtained by this method also contains 0.5% -2.5% (mole fraction) acetylene. The presence of acetylene complicates the polymerization process of ethylene, deteriorating the polymer properties. When polyethylene is produced by a high pressure process, there is a risk of explosion due to the accumulation of acetylene; in addition, the presence of acetylene also reduces the polymerization catalyst activity and increases the catalyst consumption in the production of polyethylene. It is necessary to reduce acetylene in ethylene to a certain value or less to be used as a monomer for synthesizing a polymer.
According to the separation process, ethylene units are divided into two processes: a second-carbon post-hydrogenation alkyne removal process and a second-carbon pre-hydrogenation alkyne removal process. In the two-carbon front hydrogenation process, a hydrogenation reactor is positioned in front of a demethanizer, then hydrogenation is carried out by adopting a sequential separation process, methane and ethane are removed, and then the two-carbon hydrogenation reaction is carried out, and the hydrogenation reactor is positioned behind the demethanizer. The post-hydrogenation process is mainly represented by a LUMMUS company sequential separation process technology, and the process is common in ethylene devices which are introduced in early stages in China. The front hydrogenation process is divided into a front deethanization front hydrogenation process and a front depropanization front hydrogenation process, which are respectively developed by LINDE company and S & W company, and the two processes are that acetylene is removed by selective hydrogenation before a demethanizer, but in the front depropanization front hydrogenation process, materials entering a hydrogenation reactor not only have C2 fraction but also have partial C3 fraction, and most propyne and allene need to be removed while acetylene is removed.
Principle of alkyne removal by carbon two selective hydrogenation:
the main reaction: c (C) 2 H 2 +H 2 →C 2 H 4 +174.3kJ/mol (1)
CH 3 -C≡CH+H 2 →C 3 H 6 +165kJ/mol (2)
H 2 C＝C＝CH 2 +H 2 →C 3 H 6 +173kJ/mol (3)
Side reaction: c (C) 2 H 2 +2H 2 →C 2 H 6 +311.0kJ/mol (4)
C 2 H 4 +H 2 →C 2 H 6 +136.7kJ/mol (5)
C 3 H 6 +H 2 →C 3 H 8 +136.7kJ/mol (6)
nC 2 H 2 Oligomers (green oil) (7)
Among these reactions (1) and (2) are the main reactions that are desired to take place, both to remove acetylene, propyne and propadiene and to increase ethylene and propylene. (3) (4), (5), (6) and (7) are undesirable side reactions, resulting in the loss of ethylene, propylene. A side reaction (7) of generating a carbon four fraction by the acetylene hydrodimerization reaction; polymerizing the four carbon fractions to generate oligomers with wider molecular weight, commonly called green oil; green oil is adsorbed on the catalyst surface, eventually forming coke. The cokes block the pore channels of the catalyst, so that reactants cannot diffuse to the surface of the active center of the catalyst, thereby reducing the activity of the catalyst and affecting the operation period and service life of the catalyst.
The patent US4404124 prepares a selective hydrogenation catalyst with active component palladium shell distribution by a step-by-step impregnation method, and can be applied to selective hydrogenation of carbon two and carbon three fractions so as to eliminate acetylene in ethylene and propyne and propadiene in propylene. US5587348 uses alumina as a carrier, adjusts the action of promoter silver and palladium, and adds alkali metal and chemically bonded fluorine to prepare the carbon hydrogenation catalyst with excellent performance. The catalyst has the characteristics of reducing green oil generation, improving ethylene selectivity and reducing the generation amount of oxygen-containing compounds. US5519566 discloses a method for preparing a silver and palladium catalyst by wet reduction, wherein an organic or inorganic reducing agent is added into an impregnating solution to prepare a silver and palladium two-component selective hydrogenation catalyst.
The traditional carbon two hydrogenation catalysts are prepared by adopting an impregnation method, and the active phases of the catalyst are Pd and Ag bimetallic. This method has the following disadvantages: (1) The dispersion of the active component can not be accurately controlled and the randomness is strong under the influence of the pore structure of the carrier. (2) Under the influence of the surface tension and solvation effect of the impregnating solution, the precursor of the metal active component is deposited on the surface of the carrier in an aggregate form, and uniform distribution cannot be formed. (3) The selectivity requirement of the carbon two hydrogenation on the catalyst is higher, and the traditional preparation method promotes the exertion of the auxiliary agent effect by increasing the amount of Ag, so that the transmission of hydrogen is blocked, the possibility of oligomerization is increased, the green oil generation amount is increased, and the service life of the catalyst is influenced. The occurrence of the three phenomena easily causes poor dispersibility of the metal active components, low reaction selectivity and high green oil yield, thereby affecting the overall performance of the catalyst.
CN201110086174.0 forms a polymer coating layer on the surface of a carrier by adsorbing a specific polymer compound on the carrier, and reacts with the polymer by using a compound with a functional group, so that the compound has a functional group capable of complexing with an active component, and the active component is subjected to a complexing reaction on the functional group on the surface of the carrier, thereby ensuring the ordered and high dispersion of the active component. By adopting the patent method, the carrier adsorbs a specific high molecular compound, and the hydroxyl groups of the alumina are subjected to chemical adsorption, so that the amount of the carrier adsorbed the high molecular compound is limited by the hydroxyl groups of the alumina; the complexation of the functionalized polymer and Pd is not strong, the loading amount of the active component sometimes does not meet the requirement, and part of the active component is remained in the impregnating solution, so that the cost of the catalyst is increased.
In order to improve the anti-coking performance of the catalyst and reduce the surface coking degree of the catalyst, a carbon two-selective hydrogenation catalyst adopting a bimodal pore carrier and a microemulsion preparation method to load active components and a preparation method thereof are disclosed in recent years. The selective hydrogenation catalyst disclosed in patent ZL201310114077.7 is mainly alumina and has a bimodal pore distribution structure, wherein the pore diameter of small pores is within 50nm, and the pore diameter of large pores is 60-800 nm. Based on the mass of the catalyst as 100%, the catalyst contains 0.01 to 0.5 weight percent of Pd, is distributed in a shell layer and has the thickness of 1 to 500um; the Ni-containing anti-coking component Ni is controlled to have a particle size larger than that of small holes of the carrier by a microemulsion method, so that the Ni is mainly distributed in the large holes of the carrier. Patent ZL201310114079.6 discloses a preparation method of a hydrogenation catalyst, wherein a catalyst carrier is mainly alumina and has a bimodal pore distribution structure. The catalyst contains Pd and Ni double active components, and the active component Pd is mainly distributed on the surface of a carrier, particularly in small holes, by making the anti-coking component Ni enter the carrier macropores in the form of microemulsion when preparing the catalyst. Patent ZL201310114371.8 discloses a carbon two-fraction selective hydrogenation method suitable for a pre-depropanization pre-hydrogenation process. The selective hydrogenation catalyst adopted by the method is alumina or alumina mainly, has a bimodal pore distribution structure, contains double active components Pd and Ni, and has an anti-coking component Ni mainly distributed in macropores. The method improves the coking resistance of the catalyst, but the reduction temperature of the single-component Ni in the macropores of the catalyst carrier reaches more than 500 ℃, and the single-component Ni is reduced at the reduction temperature, so that the active component Pd of the catalyst is aggregated, and the activity of the catalyst is greatly reduced. To compensate for the loss of catalyst activity, the amount of active component is increased, which results in a decrease in catalyst selectivity and a decrease in active component utilization.
Disclosure of Invention
The invention relates to an alkyne selective hydrogenation catalyst, in particular to a high coking resistance selective hydrogenation catalyst for hydrogenation before depropanization of carbon two fractions.
The catalyst of the invention is characterized in that the carrier is alumina or mainly aluminaAnd has a bimodal pore distribution structure, wherein the pore diameter of the small pores is 50-65 nm, and the pore diameter of the large pores is 250-550 nm. The specific surface area of the catalyst is 5-15 m 2 /g。
In the invention, the catalyst at least contains Pd, au, ni, cu, wherein Pd is loaded in a micro-emulsion mode and a solution mode, ni and Cu are loaded in a micro-emulsion mode, and Au is loaded in a solution mode. The content of Pd carried by the solution is 0.035-0.065%, preferably 0.037-0.045%, the weight ratio of Au to Pd carried by the solution is 1.3-3.0, preferably 1.5-2.5, the content of Ni is 0.5-8.0%, preferably 2.0-5.8, the weight ratio of Cu to Ni is 0.1-0.9, preferably 0.3-0.8, and the Pd carried by the microemulsion is 1/150-1/250, preferably 1/180-1/230 of Ni+Cu content, based on 100% of the mass of the catalyst. Wherein Ni, cu and Pd loaded by the microemulsion are mainly distributed in macropores of 250-550 nm of the carrier.
In the catalyst, the selective hydrogenation reaction of acetylene occurs in a main active center composed of Pd and Au loaded by a solution; ni and Cu are immersed in macropores of a carrier in the form of microemulsion, and green oil generated in the reaction is subjected to saturated hydrogenation on an active center composed of Cu and Ni.
For hydrogenation reaction, the hydrogenation catalyst is generally reduced before the catalyst is applied, so that the active components exist in a metal state, and the catalyst has hydrogenation activity. Because the catalyst preparation process is an elevated temperature calcination process in which the metal salt decomposes to metal oxides which form clusters, which are typically nano-sized. Different oxides, due to their different chemical properties, need to be reduced at different temperatures. However, for nano-sized metals, a critical temperature of about 200 ℃ is an important critical temperature beyond which metal particles can aggregate quite significantly. Therefore, reducing the reduction temperature of the active component is of great importance for hydrogenation catalysts.
The invention solves the problems of catalyst coking by the following steps:
alkyne selective hydrogenation reaction occurs in main active centers of components, such as Pd and Au, macromolecules such as green oil produced in the reaction, and the like, and easily enter macropores of the catalyst. In the macroporous catalyst, ni/Cu component is loaded, wherein Ni has saturated hydrogenation function, and green oil component can generate saturated hydrogenation reaction in active center of Ni/Cu component. Because the double bond is saturated by hydrogenation, the green oil component can not undergo polymerization reaction or greatly reduce the polymerization reaction rate, the chain growth reaction is terminated or delayed, a huge molecular weight condensed ring compound can not be formed, and the condensed ring compound is easily carried out of the reactor by materials, so that the coking degree of the surface of the catalyst can be greatly reduced, and the service life of the catalyst can be greatly prolonged.
The method for controlling the Ni/Cu alloy to be positioned in the macropores of the catalyst is that Ni/Cu is loaded in the form of microemulsion, and the particle size of the microemulsion is larger than the pore diameter of the micropores of the carrier and smaller than the maximum pore diameter of the macropores. Nickel and copper metal salts are contained in microemulsions and, due to steric drag, are difficult to access into the pores of smaller size supports and thus mainly into the macropores of the support.
In the invention, cu and Ni are loaded together, so that the reduction temperature of Ni can be reduced, and the reduction temperature is generally required to reach 450-500 ℃ to cause Pd agglomeration in the process of completely reducing NiO, so that after Cu/Ni alloy is formed, the reduction temperature can be reduced by more than 100 ℃ to reach 350 ℃ compared with the reduction temperature of pure Ni, thereby relieving Pd agglomeration in the reduction process.
In the invention, a small amount of Pd loaded on the microemulsion is on the surface of the Ni/Cu alloy, so that the reduction temperature of Ni can be further reduced to below 200 ℃ and at least 150 ℃.
In the invention, in the process of loading palladium by a solution method, the solution containing palladium enters the pores more quickly due to the siphoning effect of the pores, the palladium exists in the form of chloropalladate ions, and the palladium is targeted quickly due to the fact that the ions can form chemical bonds with hydroxyl groups on the surface of the carrier, so that the faster the solution enters the pore channels, the faster the loading speed is. So that it is more easily supported in the pores during impregnation of Pd in a solution method.
In the invention, the carrier is required to have a bimodal pore distribution structure, the pore diameter of the macropores is 250-550 nm, and the pores are smallThe diameter is 50-65 nm. The carrier being alumina or mainly alumina, al 2 O 3 The crystal form is preferably alpha, theta or a mixed crystal form thereof. The alumina content in the catalyst carrier is preferably 80% or more, and other metal oxides such as magnesia, titania and the like may be contained in the carrier.
In the invention, pd is loaded by adopting two modes of a solution method and a microemulsion method, namely, most Pd is loaded by adopting a solution, and the solution loading of Pd is recommended to adopt a supersaturation impregnation method; and (3) loading a small part of Pd in a microemulsion mode, wherein the particle size of the microemulsion is controlled to be larger than 65nm and smaller than 550nm when the microemulsion is loaded, so that the part of Pd is distributed in macropores of the carrier, and the step of loading the Pd in the microemulsion is performed after the step of loading the Ni and Cu in the microemulsion.
In the present invention, the loading of Au can be performed in a solution supersaturation impregnation method, and the loading thereof is performed after the loading of Pd in the solution.
The present invention is not particularly limited to the process of loading Ni, cu and Pd in the form of microemulsion, and Ni, cu and Pd can be distributed in the macropores of the carrier as long as the microemulsion can form a particle size of more than 65nm and less than 550nm.
In the invention, the weight ratio of the water phase to the oil phase is 3.0-4.5, the weight ratio of the surfactant to the oil phase is 0.15-0.5, and the weight ratio of the surfactant to the cosurfactant is 1.0-1.2.
The invention also provides a more specific catalyst, and the preparation method of the catalyst comprises the following steps:
(1) Dissolving precursor salts of Ni and Cu in water, adding an oil phase, a surfactant and a cosurfactant, and fully stirring to form microemulsion, wherein the particle size of the microemulsion is controlled to be more than 65nm and less than 550nm; adding the carrier into the prepared microemulsion, soaking for 0.5-4 hours, filtering residual liquid, drying for 1-6 hours at 80-120 ℃, and roasting for 2-8 hours at 300-600 ℃. Obtaining a semi-finished catalyst A;
(2) Dissolving Pd precursor salt in water, regulating the pH value to be 1.5-2.5, adding the semi-finished catalyst A into Pd salt solution, soaking and adsorbing for 0.5-4 h, drying for 1-4 h at 80-120 ℃, and roasting for 2-6 h at 400-550 ℃ to obtain a semi-finished catalyst B;
(3) The Au is loaded by a supersaturation impregnation method, namely, the prepared chloroauric acid solution is 80-110% of the saturated water absorption rate of the carrier, the pH value is adjusted to be 1-5, and the semi-finished catalyst B is baked at 500-550 ℃ for 4-6 hours after the Au is loaded, so as to obtain the semi-finished catalyst C;
(4) Dissolving Pd precursor salt in water, adding an oil phase, a surfactant and a cosurfactant, and fully stirring to form microemulsion, wherein the particle size of the microemulsion is controlled to be more than 65nm and less than 550nm; adding the semi-finished catalyst C into the prepared microemulsion, soaking for 0.5-4 hours, and filtering out residual liquid; drying at 80-120 deg.c for 1-6 hr and roasting at 300-600 deg.c for 2-8 hr to obtain the catalyst.
In the above preparation steps, the step (1) and the step (2) may be interchanged, the step (3) follows the step (2), and the step (4) follows the step (1).
The carrier in the step (1) can be spherical, cylindrical, clover-shaped, tooth-shaped, clover-shaped and the like.
The precursor salts of Ni, cu, au and Pd in the above steps are soluble salts, and can be nitrate salts, chloride salts or other soluble salts thereof.
The reduction temperature of the catalyst of the present invention is preferably 150 to 200 ℃.
The catalyst has the following characteristics: at the beginning of the hydrogenation reaction, the selective hydrogenation reaction of acetylene mainly occurs in the pores because palladium has high hydrogenation activity and is mainly distributed in the pores. With the extension of the catalyst running time, a part of byproducts with larger molecular weight are generated on the surface of the catalyst, and the substances enter the macropores more due to larger molecular size, and the stay time is longer, so that double bond hydrogenation reaction can occur under the action of the nickel catalyst, saturated hydrocarbon or aromatic hydrocarbon without isolated double bonds is generated, and substances with larger molecular weight are not generated.
The catalyst prepared by the method has the advantages that the initial activity and the selectivity of the catalyst are obviously improved compared with those of the traditional catalyst.
The catalyst of the invention has the advantages that even if the raw materials contain more heavy fractions, the green oil production amount of the catalyst is greatly increased, and the activity and selectivity of the catalyst still have no tendency to be reduced.
Drawings
FIG. 1 is a graph showing the peak reduction temperature of Ni/Cu in example 1.
Fig. 2 is a flow chart of a carbon di-hydrogenation process using a pre-depropanization process.
In the figure: 1-an oil washing tower; 2-a water washing tower; 3-an alkaline washing tower; 4-a dryer; 5-a front-end depropanizer; a 6-carbon two front hydrogenation reactor; 7-a demethanizer; 8-a heat exchanger.
Detailed Description
The following describes embodiments of the present invention in detail: the present example is implemented on the premise of the technical scheme of the present invention, and detailed implementation modes and processes are given, but the protection scope of the present invention is not limited to the following examples, and experimental methods without specific conditions are not noted in the following examples, and generally according to conventional conditions.
The analytical test method comprises the following steps:
the ratio table: GB/T-5816;
pore volume: GB/T-5816;
the catalyst contains active components: atomic absorption;
microemulsion particle size distribution of Ni/Cu alloy: a dynamic light scattering particle size analyzer, on an M286572 dynamic light scattering analyzer;
the conversion and selectivity in the examples were calculated according to the following formulas:
acetylene conversion (%) =100× delta acetylene/inlet acetylene content
Ethylene selectivity (%) =100×Δethylene/Δacetylene
Example 1
And (3) a carrier: the commercial bimodal pore distribution spherical alumina carrier with the diameter of 4mm is adopted, and the mixture is roasted for 4 hours at high temperature, and 100g of the mixture is weighed. The calcination temperature and the physical properties of the carrier are shown in Table 1.
And (3) preparing a catalyst:
(1) Weighing a certain amount of nickel nitrate and copper chloride, dissolving the nickel nitrate and copper chloride in deionized water, adding a certain amount of cyclohexane, triton X-100 and n-butanol, fully stirring to form microemulsion, dipping 100g of the weighed carrier into the prepared microemulsion for 1 hour, washing the carrier to be neutral by deionized water, drying the carrier at 120 ℃ for 2 hours, and roasting the carrier at 550 ℃ for 5 hours. To obtain a semi-finished catalyst A.
(2) Weighing a certain amount of palladium nitrate, dissolving in deionized water, adjusting the pH to 1, soaking the semi-finished catalyst A in the prepared Pd salt solution, adsorbing for 1h, drying at 110 ℃ for 2h, and roasting at 380 ℃ for 6h to obtain the semi-finished catalyst B.
(3) Weighing chloroauric acid, preparing into a solution by using deionized water, adding the semi-finished catalyst B into the solution, shaking, drying at 110 ℃ for 3 hours after the solution is completely absorbed, and roasting at 500 ℃ for 4 hours to obtain the required catalyst.
The particle size of the microemulsion prepared in the catalyst preparation process and the content of each component in the catalyst are shown in table 2.
Before use, the mixture is placed in a fixed bed reaction device, and the molar ratio is N 2 :H 2 Mixed gas of=1:1, at 350 ℃, reduction treatment for 12h.
Example 2
And (3) a carrier: adopts a commercial bimodal pore distribution spherical carrier with the diameter of 4mm, and the composition of the carrier is 90 percent of alumina and 10 percent of titanium oxide. After roasting for 4 hours at high temperature, 100g of the carrier is weighed, and physical properties of the carrier are shown in Table 1.
And (3) preparing a catalyst:
(1) Weighing nickel nitrate with certain mass, dissolving copper chloride in deionized water, adding certain cyclohexane, tritonX-100 and n-hexanol, and fully stirring to form microemulsion. The carrier is added into the prepared microemulsion to be immersed for 1 hour, then washed to be neutral by deionized water, dried for 2 hours at 120 ℃, and baked for 5 hours at 550 ℃. To obtain a semi-finished catalyst A.
(2) A certain amount of palladium nitrate is weighed and dissolved in water, a certain amount of cyclohexane, tritonX-100 and 6.03g of n-hexanol are added and fully stirred to form microemulsion. And (3) adding the semi-finished catalyst A into the prepared microemulsion, soaking for 4 hours, washing with deionized water to neutrality, drying at 90 ℃ for 4 hours, and roasting at 600 ℃ for 2 hours to obtain the semi-finished catalyst B.
(3) And (3) weighing a certain amount of palladium nitrate, dissolving in water, adjusting the pH to be 2, adding the semi-finished product B into a Pd salt solution, soaking and adsorbing for 1h, drying at 110 ℃ for 2h, and roasting at 380 ℃ for 6h to obtain the semi-finished product catalyst C.
(4) Weighing a certain amount of chloroauric acid, dissolving in deionized water, immersing the semi-finished catalyst C in the prepared solution, drying at 110 ℃ for 3 hours, and roasting at 500 ℃ for 4 hours to obtain the finished catalyst.
The particle size of the microemulsion prepared in the catalyst preparation process and the content of each component in the catalyst are shown in table 2.
Before use, the mixture is placed in a fixed bed reaction device, and the molar ratio is N 2 :H 2 Mixed gas of 1:1, at 200 ℃, reduction treatment for 12h.
Example 3
And (3) a carrier: a commercially available bimodal pore distribution spherical alumina carrier was used, 4mm in diameter. After 4 hours of high temperature calcination, 100g of the carrier is weighed, and physical indexes are shown in Table 1.
And (3) preparing a catalyst:
(1) And (3) weighing a certain amount of palladium nitrate, dissolving in water, adjusting the pH to be 2, adding the carrier into a Pd salt solution, soaking and adsorbing for 1h, drying at 110 ℃ for 2h, and roasting at 380 ℃ for 6h to obtain the semi-finished catalyst A.
(2) Weighing a certain amount of chloroauric acid, dissolving in deionized water, immersing the semi-finished catalyst A in the prepared solution, drying at 110 ℃ for 3 hours, and roasting at 500 ℃ for 4 hours to obtain the semi-finished catalyst B.
(3) A certain amount of nickel nitrate and copper chloride are weighed and dissolved in water, a certain amount of cyclohexane and TritonX-100 and 6.03g of n-hexanol are added and fully stirred to form microemulsion. The semi-finished catalyst B is added into the prepared microemulsion to be immersed for 4 hours, then washed to be neutral by deionized water, dried for 4 hours at 90 ℃, and baked for 2 hours at 600 ℃. Semi-finished catalyst C is obtained.
(4) A certain amount of palladium nitrate is weighed and dissolved in water, a certain amount of cyclohexane, tritonX-100 and 6.03g of n-hexanol are added and fully stirred to form microemulsion. The semi-finished catalyst C is added into the prepared microemulsion to be immersed for 4 hours, then washed to be neutral by deionized water, dried for 4 hours at 90 ℃, and baked for 2 hours at 600 ℃. Obtaining the finished catalyst.
The particle size of the microemulsion prepared in the catalyst preparation process and the content of each component in the catalyst are shown in table 2.
Before use, the mixture is placed in a fixed bed reaction device, and the molar ratio is N 2 :H 2 Mixed gas of 1:1, at 160 ℃, reduction treatment for 12h.
Example 4
And (3) a carrier: a commercially available bimodal pore distribution spherical alumina carrier was used, 4mm in diameter. After 4 hours of high temperature calcination, 100g of the carrier is weighed, and physical indexes are shown in Table 1.
And (3) preparing a catalyst:
(1) A certain amount of nickel nitrate and copper chloride are weighed and dissolved in water, a certain amount of cyclohexane and TritonX-100 and 6.03g of n-hexanol are added and fully stirred to form microemulsion. The carrier is added into the prepared microemulsion to be immersed for 4 hours, then washed to be neutral by deionized water, dried for 4 hours at 90 ℃, and baked for 2 hours at 600 ℃. To obtain a semi-finished catalyst A.
(2) And (3) weighing a certain amount of palladium nitrate, dissolving in water, adjusting the pH value to be 2, adding the semi-finished catalyst A into a Pd salt solution, soaking and adsorbing for 1h, drying at 110 ℃ for 2h, and roasting at 380 ℃ for 6h to obtain the semi-finished catalyst B.
(3) Weighing a certain amount of chloroauric acid, dissolving in deionized water, immersing the semi-finished catalyst B in the prepared solution, drying at 110 ℃ for 3 hours, and roasting at 500 ℃ for 4 hours to obtain the semi-finished catalyst C.
(4) A certain amount of palladium nitrate is weighed and dissolved in water, a certain amount of cyclohexane, tritonX-100 and 6.03g of n-hexanol are added and fully stirred to form microemulsion. The semi-finished catalyst C is added into the prepared microemulsion to be immersed for 4 hours, then washed to be neutral by deionized water, dried for 4 hours at 90 ℃, and baked for 2 hours at 600 ℃. Obtaining the finished catalyst.
The particle size of the microemulsion prepared in the catalyst preparation process and the content of each component in the catalyst are shown in table 2.
Before use, the mixture is placed in a fixed bed reaction device, and the molar ratio is N 2 :H 2 Mixed gas of 1:1, at 170 ℃, reduction treatment for 12h.
Example 5
And (3) a carrier: a commercially available bimodal pore distribution spherical alumina carrier was used, 4mm in diameter. After 4 hours of high temperature calcination, 100g of the carrier is weighed, and physical indexes are shown in Table 1.
And (3) preparing a catalyst:
(1) A certain amount of nickel nitrate and copper chloride are weighed and dissolved in water, a certain amount of cyclohexane and TritonX-100 and 6.03g of n-hexanol are added and fully stirred to form microemulsion. The carrier is added into the prepared microemulsion to be immersed for 4 hours, then washed to be neutral by deionized water, dried for 4 hours at 90 ℃, and baked for 2 hours at 600 ℃. To obtain a semi-finished catalyst A.
(2) A certain amount of palladium nitrate is weighed and dissolved in water, a certain amount of cyclohexane, tritonX-100 and 6.03g of n-hexanol are added and fully stirred to form microemulsion. The semi-finished catalyst A is added into the prepared microemulsion to be immersed for 4 hours, then washed to be neutral by deionized water, dried for 4 hours at 90 ℃, and baked for 2 hours at 600 ℃. Semi-finished catalyst B was obtained.
(3) And (3) weighing a certain amount of palladium nitrate, dissolving in water, adjusting the pH to be 2, adding the semi-finished catalyst B into a Pd salt solution, soaking and adsorbing for 1h, drying at 110 ℃ for 2h, and roasting at 380 ℃ for 6h to obtain a semi-finished catalyst C.
(4) Weighing a certain amount of chloroauric acid, dissolving in deionized water, immersing the semi-finished catalyst C in the prepared solution, drying at 110 ℃ for 3 hours, and roasting at 500 ℃ for 4 hours to obtain the finished catalyst.
The particle size of the microemulsion prepared in the catalyst preparation process and the content of each component in the catalyst are shown in table 2.
Before use, the mixture is placed in a fixed bed reaction device, and the molar ratio is N 2 :H 2 Mixed gas of 1:1, at 150 ℃, reduction treatment for 12h.
Comparative example 1
And (3) a carrier: a commercially available bimodal pore distribution spherical alumina carrier was used, 4mm in diameter. After 4 hours of high temperature calcination, 100g of the carrier is weighed, and physical indexes are shown in Table 1.
And (3) preparing a catalyst:
(1) A certain amount of nickel nitrate is weighed and dissolved in 70ml of deionized water, a certain amount of cyclohexane, triton X-100 and n-butanol are added, the mixture is fully stirred to form microemulsion, the carrier is immersed into the prepared microemulsion for 1 hour, and then washed to be neutral by the deionized water, dried for 2 hours at 120 ℃, and baked for 5 hours at 550 ℃. Semi-finished catalyst A1 was obtained.
(2) Weighing a certain amount of palladium nitrate, dissolving in deionized water, adjusting the pH to 1, soaking the semi-finished catalyst A in the prepared Pd salt solution, adsorbing for 1h, drying at 110 ℃ for 2h, and roasting at 380 ℃ for 6h to obtain a semi-finished catalyst B1.
(3) Weighing chloroauric acid, preparing into solution by deionized water, immersing the semi-finished catalyst B1 into the prepared solution, shaking, drying at 110 ℃ for 3 hours after the solution is completely absorbed, and roasting at 500 ℃ for 4 hours to obtain the required catalyst.
The particle size of the microemulsion prepared in the catalyst preparation process and the content of each component in the catalyst are shown in table 2.
Before use, the mixture is placed in a fixed bed reaction device, and the molar ratio is N 2 :H 2 Mixed gas of =1:1, at 500 ℃, reduction treatment is carried out for 12h.
Comparative example 2
And (3) a carrier: adopts a commercial bimodal pore distribution spherical carrier with the diameter of 4mm, and the composition of the carrier is 90 percent of alumina and 10 percent of titanium oxide. After 4 hours of high temperature calcination, 100g of the carrier is weighed, and physical indexes are shown in Table 1.
And (3) preparing a catalyst:
(1) A certain amount of nickel nitrate is weighed, copper nitrate is dissolved in deionized water, a certain amount of cyclohexane is added, 14.3g of Triton X-100 and 13.60g of n-hexanol are fully stirred to form microemulsion. The carrier is added into the prepared microemulsion to be immersed for 1 hour, then washed to be neutral by deionized water, dried for 2 hours at 120 ℃, and baked for 5 hours at 550 ℃. Semi-finished catalyst A1 was obtained.
(2) And (3) weighing a certain amount of palladium nitrate, dissolving in water, adjusting the pH to 2, adding the semi-finished catalyst A1 into a Pd salt solution, soaking and adsorbing for 1h, drying at 110 ℃ for 2h, and roasting at 380 ℃ for 6h to obtain the finished catalyst.
The particle size of the microemulsion prepared in the catalyst preparation process and the content of each component in the catalyst are shown in table 2.
Before use, the mixture is placed in a fixed bed reaction device, and the molar ratio is N 2 :H 2 Mixed gas of=1:1, at 350 ℃, reduction treatment for 12h.
Comparative example 3
And (3) a carrier: a commercially available unimodal pore distributed spherical alumina carrier was used, 4mm in diameter. After 4 hours of high temperature calcination, 100g of the carrier is weighed, and physical indexes are shown in Table 1.
And (3) preparing a catalyst:
(1) And (3) weighing a certain amount of palladium chloride salt, dissolving in water, adjusting the pH to 3, adding the weighed carrier into a Pd salt solution, soaking and adsorbing for 2 hours, drying at 120 ℃ for 1 hour, and roasting at 450 ℃ for 4 hours to obtain the semi-finished catalyst A1.
(2) Weighing a certain amount of chloroauric acid, dissolving in deionized water, immersing the semi-finished catalyst A1 in the prepared solution, drying at 100 ℃ for 4 hours, and roasting at 400 ℃ for 6 hours until the solution is completely absorbed to obtain the required catalyst.
The content of each component in the catalyst is shown in Table 2.
Before use, the mixture is placed in a fixed bed reaction device, and the molar ratio is N 2 :H 2 Mixed gas of=1:1, at 350 ℃, reduction treatment for 12h.
Comparative example 4
And (3) a carrier: a commercially available bimodal pore distribution spherical alumina carrier was used, 4mm in diameter. After 4 hours of high temperature calcination, 100g of the carrier is weighed, and physical indexes are shown in Table 1.
And (3) preparing a catalyst:
(1) And (3) weighing a certain amount of palladium nitrate, dissolving in water, adjusting the pH to be 2, adding the carrier into a Pd salt solution, soaking and adsorbing for 1h, drying at 110 ℃ for 2h, and roasting at 380 ℃ for 6h to obtain the semi-finished catalyst A.
(2) Weighing a certain amount of chloroauric acid, dissolving in deionized water, adding the semi-finished catalyst A into the prepared solution, drying at 110 ℃ for 3 hours, and roasting at 500 ℃ for 4 hours to obtain the semi-finished catalyst B.
(3) A certain amount of nickel nitrate and ferric chloride are weighed and dissolved in water, a certain amount of cyclohexane and TritonX-100 and 6.03g of n-hexanol are added and fully stirred to form microemulsion. The semi-finished catalyst B is added into the prepared microemulsion to be immersed for 4 hours, then washed to be neutral by deionized water, dried for 4 hours at 90 ℃, and baked for 2 hours at 600 ℃. Obtaining the finished catalyst.
The particle size of the microemulsion prepared in the catalyst preparation process and the content of each component in the catalyst are shown in table 2.
Before use, the mixture is placed in a fixed bed reaction device, and the molar ratio is N 2 :H 2 Mixed gas of=1:1, at 350 ℃, reduction treatment for 12h.
Table 1 physical properties of catalyst carriers of examples and comparative examples
Table 2 catalyst active ingredient content for examples and comparative examples
The above catalyst was evaluated for performance in a fixed bed reactor. Reaction conditions: airspeed 14000h -1 The pressure is 2.5MPa. The composition of the reaction mass is shown in Table 3.
TABLE 3 reaction mass composition
Table 4 results of catalyst evaluation
Of course, the present invention is capable of other various embodiments and its several details are capable of modification and variation in light of the present invention by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (13)

1. A catalyst for the hydrogenation before the front depropanization of two carbon fractions is characterized in that the carrier is alumina or alumina mainly and has a bimodal pore distribution structure, wherein the pore diameter of small pores is 50-65 nm, the pore diameter of large pores is 250-550 nm, and the specific surface area of the catalyst is 5-15 m 2 /g; the catalyst at least contains Pd, au, ni, cu, wherein Pd is loaded in a micro-emulsion mode and a solution mode, ni and Cu are loaded in a micro-emulsion mode, and Au is loaded in a solution mode; based on the mass of the catalyst being 100%, the Pd content loaded by the solution is 0.035-0.065%, the weight ratio of Au to Pd loaded by the solution is 1.3-3.0, the Ni content is 0.5-8.0%, and the weight ratio of Cu to Ni is 0.1-0.9; wherein Ni, cu and Pd loaded by the microemulsion are mainly distributed in the macropores of 250-550 nm of the carrier;
wherein, most Pd is loaded by solution, and a small part Pd is loaded by microemulsion, so that the small part Pd is distributed in the macropores of the carrier.
2. The catalyst according to claim 1, wherein the content of Pd supported in the solution is 0.037 to 0.045%, the weight ratio of Au to Pd supported in the solution is 1.5 to 2.5, the content of Ni is 2.0 to 5.8, and the weight ratio of Cu to Ni is 0.3 to 0.8, based on 100% by mass of the catalyst.
3. Catalyst according to claim 1, characterized in that the solution loading of Pd, au is carried out in supersaturated impregnation.
4. The catalyst according to claim 1, wherein the Pd content of the microemulsion is 1/150 to 1/250 of the Ni+Cu content.
5. The catalyst of claim 4 wherein the microemulsion has a Pd content of 1/180 to 1/230 of the Ni+Cu content.
6. The catalyst of claim 1, wherein the microemulsion loading process comprises: dissolving precursor salt in water, adding an oil phase, a surfactant and a cosurfactant, and fully stirring to form microemulsion, wherein the oil phase is C6-C8 saturated alkane or naphthene; the surfactant is an ionic surfactant and/or a nonionic surfactant; the cosurfactant is C4-C6 organic alcohols.
7. The catalyst according to claim 6, wherein the oil phase is cyclohexane and/or n-hexane, the surfactant is polyethylene glycol octyl phenyl ether and/or cetyl trimethyl ammonium bromide, and the cosurfactant is n-butanol and/or n-pentanol.
8. The catalyst of claim 6 wherein the microemulsion has a weight ratio of water phase to oil phase of 3.0 to 4.5, a weight ratio of surfactant to oil phase of 0.15 to 0.5, and a weight ratio of surfactant to cosurfactant of 1.0 to 1.2.
9. Catalyst according to claim 1, characterized in that during the preparation of the catalyst the step of loading the microemulsion with Pd is after the step of loading the microemulsion with Ni and Cu.
10. The catalyst according to claim 1, wherein the solution-process loading of Pd and the loading sequencing of Ni/Cu are not limited during the preparation process.
11. The catalyst according to claim 1, wherein during the preparation of the catalyst, the step of loading Au by a solution method is performed after the step of loading Pd by a solution method.
12. The catalyst according to claim 1, wherein the catalyst is alumina or mainly alumina; al (Al) 2 O 3 The crystal forms are theta, alpha or a mixed crystal form thereof; the mass fraction of alumina in the carrier is more than 80%.
13. Catalyst according to claim 1, characterized in that the catalyst preparation process comprises in particular the following steps:
(1) 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 more than 65nm and less than 550nm, adding a carrier into the prepared microemulsion, soaking for 0.5-4 hours, filtering out residual liquid, drying at 60-120 ℃ for 1-6 hours, and roasting at 300-600 ℃ for 2-8 hours to obtain a semi-finished catalyst A;
(2) Dissolving Pd precursor salt in water, regulating the pH value to be 1.5-2.5, adding the semi-finished catalyst A into Pd salt solution, soaking and adsorbing for 0.5-4 h, drying for 1-4 h at 100-120 ℃, and roasting for 2-6 h at 400-550 ℃ to obtain a semi-finished catalyst B;
(3) The loading of Au is carried out by a saturated dipping method, namely, the prepared Au salt solution is 80-110% of the saturated water absorption rate of the carrier, the pH value is adjusted to be 1-5, and the semi-finished catalyst B is baked at 500-550 ℃ for 4-6 hours after loading the Au to obtain the semi-finished catalyst C;
(4) Dissolving Pd precursor salt in water, adding an oil phase, a surfactant and a cosurfactant, fully stirring to form microemulsion, controlling the particle size of the microemulsion to be more than 65nm and less than 550nm, adding a semi-finished catalyst C into the prepared microemulsion, soaking for 0.5-4 hours, filtering out residual liquid, drying at 60-120 ℃ for 1-6 hours, and roasting at 300-600 ℃ for 2-8 hours to obtain the required catalyst.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4490481A (en) * 1982-03-15 1984-12-25 Ste Francaise Des Produits Pour Catalyse Chez Institut Francais Du Petrole Supported palladium-gold catalyst, and its manufacture
CN103071490A (en) * 2011-10-26 2013-05-01 中国石油化工股份有限公司 Palladium catalyst used in unsaturated hydrocarbon hydrogenation, and application thereof
CN103084172A (en) * 2011-10-28 2013-05-08 中国石油化工股份有限公司 C2 fraction selective hydrogenation catalyst, preparation method and applications thereof
CN104098425A (en) * 2013-04-03 2014-10-15 中国石油天然气股份有限公司 C2 fraction selective hydrogenation method
CN104098426A (en) * 2013-04-03 2014-10-15 中国石油天然气股份有限公司 C2 fraction selective-hydrogenation method
CN108014792A (en) * 2016-11-02 2018-05-11 中国石油化工股份有限公司 A kind of Ethylene Fraction Selective Hydrogenation, preparation method and application

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4490481A (en) * 1982-03-15 1984-12-25 Ste Francaise Des Produits Pour Catalyse Chez Institut Francais Du Petrole Supported palladium-gold catalyst, and its manufacture
CN103071490A (en) * 2011-10-26 2013-05-01 中国石油化工股份有限公司 Palladium catalyst used in unsaturated hydrocarbon hydrogenation, and application thereof
CN103084172A (en) * 2011-10-28 2013-05-08 中国石油化工股份有限公司 C2 fraction selective hydrogenation catalyst, preparation method and applications thereof
CN104098425A (en) * 2013-04-03 2014-10-15 中国石油天然气股份有限公司 C2 fraction selective hydrogenation method
CN104098426A (en) * 2013-04-03 2014-10-15 中国石油天然气股份有限公司 C2 fraction selective-hydrogenation method
CN108014792A (en) * 2016-11-02 2018-05-11 中国石油化工股份有限公司 A kind of Ethylene Fraction Selective Hydrogenation, preparation method and application

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
洪润润.负载型高分散Pd基催化剂制备及蒽醌加氢性能研究.《中国优秀博硕士学位论文全文数据库(博士) 工程科技Ⅰ辑》.2018,(第2期),第5.3节. *
陈玉 等.反应条件对Cu-Ni/Al2O3催化剂乙炔选择加氢的影响.《石化技术与应用》.2012,第30卷(第6期),摘要，第2.1节. *

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