CN112939723B

CN112939723B - Alkyne removing method for carbon three-fraction selective hydrogenation process

Info

Publication number: CN112939723B
Application number: CN201911186974.2A
Authority: CN
Inventors: 谭都平; 路全能; 王喆; 李保江; 何磊; 何超; 张小宇; 张生芳; 沈健明; 周文远
Original assignee: Petrochina Co Ltd
Current assignee: Petrochina Co Ltd
Priority date: 2019-11-26
Filing date: 2019-11-26
Publication date: 2023-01-10
Anticipated expiration: 2039-11-26
Also published as: CN112939723A

Abstract

The invention relates to a selective hydrogenation method for carbon three-fraction. And (2) selectively hydrogenating and refining the propyne (MA) and the Propadiene (PD) in the material by using a Pd-Rh-Ni-Cu hydrogenation catalyst. Reaction conditions are as follows: the inlet temperature of the reactor is 30-50 ℃, the reaction pressure is 1.5-3.5 MPa, and the liquid phase space velocity is 15-120 h ^‑1 hydrogen/MAPD =1 to 10; preferred hydrogenation conditions are: the inlet temperature of the adiabatic bed reactor is 30-50 ℃, the reaction pressure is 2-3 MPa, and the liquid phase space velocity is 30-60 h ^‑1 And hydrogen/propyne allene 1.1-3.0. The catalyst support is alumina or primarily alumina and has a bimodal pore distribution structure. The catalyst at least contains Pd, rh, ni and Cu, wherein the Pd is loaded in a micro-emulsion mode and a solution mode, the Ni and the Cu are loaded in the micro-emulsion mode, and the Rh is loaded in the solution mode. Wherein, the Ni, cu and Pd loaded by the microemulsion are mainly distributed in the macropores of the carrier. The catalyst has lower reduction temperature, low green oil generation amount and excellent catalytic performance and coking resistance.

Description

Alkyne removing method for carbon three-fraction selective hydrogenation process

Technical Field

The invention relates to a selective hydrogenation method for a carbon three-fraction, in particular to a method for converting propyne (MA) and Propadiene (PD) contained in the carbon three-fraction into propylene by selective hydrogenation of a Pd-Rh-Ni-Cu catalyst.

Background

Propylene, one of the most important basic raw materials in the petrochemical industry, is an important monomer for synthesizing various polymers, and is mostly prepared by steam cracking of petroleum hydrocarbons (such as ethane, propane, butane, naphtha, light diesel oil, and the like). Propylene-based C obtained by this method ₃ The fraction contains 1.5 to 8.0% of Propyne (PD) + propadiene (MA). The presence of MAPD, which affects the quality of the polymer product, is currently removed by selective hydrogenation in the petrochemical industry.

The traditional carbon-three hydrogenation catalyst adopts Al as the catalyst ₂ O ₃ As carrier, pd as active component and Ag as auxiliary active component, and the specific surface area of the catalyst is 15-100 m ² (iv) g. The preparation method of the catalyst adopts an impregnation method. The influence of the surface tension of the impregnation liquid and the solvation effect is particularly obvious in the process of impregnating and drying the catalyst, and the precursor of the metal active component is deposited on the surface of the carrier in the form of aggregates. In addition, the distribution state between Pd and Ag is not ideal, the activity of the catalyst is not easy to control, the selectivity of the catalyst is mainly controlled by the aperture of the catalyst and the dispersion state of the active components, and the dispersion randomness of the active components of the catalyst is high and the preparation repeatability is poor because the dispersion of the active components is influenced by the number of groups on the surface of the carrier and the solvation in the preparation process of the catalyst, so that the effect of the catalytic reaction is not ideal.

CN98810096 discloses a catalytic distillation method to remove MAPD in carbon three-fraction, which combines catalytic hydrogenation and rectification separation processes into one, because the heat exchange is sufficient in the process, temperature runaway is not easy to occur, and a small amount of oligomer generated in the process is easy to carry out, and the coking degree on the surface of the catalyst is greatly reduced. The method has high filling requirement on the catalytic distillation tower, and the distribution state of the fluid has great influence on the separation effect. The method also increases the difficulty of operation.

Patent No. cn201110086151.X discloses a selective hydrogenation method for carbon three-fraction, which adopts a catalyst comprising Pd as a main active component, alumina as a carrier, and a promoter silver. The carrier is adsorbed with a specific high molecular compound, a high molecular coating layer is formed on the surface of the carrier in a certain thickness, the compound with a functional group reacts with the high molecular compound to enable the compound to have the functional group capable of being complexed with the active component, and the active component is ensured to be orderly and highly dispersed by the complexation reaction of the active component on the surface of the carrier. By adopting the method, the carrier adsorbs specific high molecular compounds, and the high molecular compounds are chemically adsorbed with the high molecular compounds through the hydroxyl groups of the alumina, and the amount of the high molecular compounds adsorbed by the carrier is limited by the number of the hydroxyl groups of the alumina; the functional polymer and Pd have weak complexing effect, sometimes the loading capacity of the active components can not meet the requirement, and part of the active components are remained in the impregnation liquid, so that the cost of the catalyst is increased; the method for preparing the carbon three hydrogenation catalyst also has the defect of complex process flow.

CN2005800220708.2 discloses a selective hydrogenation catalyst for acetylene and diolefin in light olefin raw material, said catalyst is formed from first component selected from copper, gold and silver and second component selected from nickel, platinum, palladium, iron, cobalt, ruthenium and rhodium, in addition, said catalyst also includes at least one inorganic salt and oxide selected from zirconium, lanthanide and alkaline earth metal mixture. The catalyst forms a fluorite structure after being calcined, used or regenerated. The total content of the catalyst oxide is 0.01-50%, and the preferred roasting temperature is 700-850 ℃. The addition of a third oxide, modified alumina or silica support, helps to increase catalyst selectivity and activity, selectivity after regeneration. The technology still takes copper, gold, silver, palladium and the like as active components and takes nickel, platinum, palladium, iron, cobalt, ruthenium, rhodium and the like as auxiliary components, and the regeneration performance of the catalyst is improved by modifying the oxide of the carrier.

CN102218323A discloses a hydrogenation catalyst for unsaturated hydrocarbon, the active component is a mixture of 5-15% of nickel oxide and 1-10% of other metal oxides, the other metal oxides can be one or more of molybdenum oxide, cobalt oxide and iron oxide, and in addition, 1-10% of auxiliary agent is also included. The technology is mainly used for hydrogenating and converting ethylene, propylene, butylene and the like in the tail gas of the coal-to-liquid industry into saturated hydrocarbon, and has good deep hydrogenation capacity. The technology is mainly used for the total hydrogenation of ethylene, propylene, butylene and the like in various industrial tail gases rich in CO and hydrogen, and is not suitable for the selective hydrogenation of alkyne and dialkene.

CN98810096 discloses a catalytic distillation method to remove MAPD in the carbon three-fraction, which combines the catalytic hydrogenation and rectification separation processes into one, because the heat exchange is sufficient in the process, the temperature runaway is not easy to occur, and a small amount of oligomer generated in the process is easy to carry out, and the coking degree on the surface of the catalyst is greatly reduced. The method has high filling requirement on the catalytic distillation tower, and the distribution state of the fluid has great influence on the separation effect. The method also increases the difficulty of operation.

CN200810114744.0 invented an unsaturated hydrocarbon selective hydrogenation catalyst and its preparation method. The catalyst uses alumina as a carrier, uses palladium as an active component, and improves the impurity resistance and the coking resistance of the catalyst by adding rare earth, alkaline earth metal and fluorine, but the selectivity of the catalyst is not ideal.

ZL201310114077.7 discloses a hydrogenation catalyst, wherein the active components in the catalyst comprise Pd, ag and Ni, wherein the Pd and the Ag 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/Ag 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 usually about 500 ℃, and the reduced Pd atoms are easy to gather at the temperature, so that the activity of the catalyst is greatly reduced, the equivalent amount of active components needs to be greatly increased to compensate the activity loss, and the selectivity is reduced.

Disclosure of Invention

The invention aims to provide a selective hydrogenation method, in particular to a selective hydrogenation method of a carbon three-fraction hydrogenation process with high coking resistance.

The invention aims to provide an alkyne removal method for a selective hydrogenation process. In particular to a method for selectively hydrogenating and converting propyne (MA) and Propadiene (PD) contained in a carbon three-cut fraction into propylene by using a Pd-Rh-Ni-Cu catalyst in a carbon three-cut hydrogenation process without loss of the propylene.

The invention provides a selective hydrogenation method of carbon three-fraction, which is characterized in that propyne and propadiene contained in materials are selectively hydrogenated and converted into propylene in a single-stage adiabatic bed reactor.

The invention provides a selective hydrogenation method of carbon three-fraction, which is characterized in that propyne and allene contained in materials are selectively hydrogenated and converted into propylene in a single-stage adiabatic bed reactor. The hydrogenation raw material comes from a sequential separation process, and the material composition is as follows: 70 to 90 percent of propylene, 5 to 30 percent of propane, 2.0 to 5.0 percent of propine and propadiene; when the content of the propine and the propadiene is less than or equal to 4.0 percent, adopting a single-section adiabatic reactor, and when the content of the propine and the propadiene is more than 4.0 percent, adopting two sections of adiabatic reactors connected in series; or the hydrogenation raw material is from a front-end depropanization front-end hydrogenation process, and the material composition (volume ratio) is as follows: 80-95% of propylene, 5-20% of propane, 0.05-0.2% of propyne and 0.05-0.2% of propadiene, and a single-section adiabatic reactor is adopted. The hydrogenation reaction conditions are as follows: the inlet temperature of the reactor is 30-50 ℃, the reaction pressure is 1.5-3.5 MPa, and the liquid phase space velocity is 15-120 h ^-1 hydrogen/MAPD (molar ratio) =1 to 10; preferred hydrogenation conditions are: the inlet temperature of the adiabatic bed reactor is 30-50 ℃, the reaction pressure is 2-3 MPa, and the liquid phase space velocity is 30-60 h ^-1 The molar ratio of hydrogen to propadiene is 1.1-3.0.

The invention provides a selective hydrogenation method of carbon three-fraction, wherein the catalyst carrier is alumina or mainly alumina, and has a bimodal pore distribution structure, and the specific surface area of the catalyst is 20-50 m ² (ii) in terms of/g. Wherein the aperture of the small hole is 15-35 nm, and the aperture of the large hole is 70-300 nm. The catalyst at least contains Pd, rh, ni and Cu, wherein the Pd is loaded in a micro-emulsion mode and a solution mode, the Ni and the Cu are loaded in the micro-emulsion mode, and the Rh is loaded in the solution mode. The content of the solution loaded Pd is 0.25-0.40%, preferably 0.30-0.35%, the weight ratio of Rh to the solution loaded Pd is 1.5-6.0, preferably 2.0-4.5%, the content of Ni is 5.0-10%, preferably 6.8-8.0%, the weight ratio of Cu to Ni is 0.1-1.0, preferably 0.4-0.8%, and the content of the microemulsion loaded Pd is 1/100-1/200, preferably 1/120-1/150 of the Ni + Cu content, based on 100% of the mass of the catalyst. Wherein, the Ni, cu and Pd loaded by the microemulsion are mainly distributed in macropores of 35-300 nm of the carrier.

In the catalyst, the selective hydrogenation reaction of alkyne takes place in the main active center composed of Pd and Rh, ni and Cu are dipped in the macropores of the carrier in the form of microemulsion, and the green oil generated in the reaction is subjected to saturated hydrogenation on the active center composed of Cu and Ni.

The Cu has the function of forming Ni/Cu alloy in the roasting process, effectively reduces the reduction temperature of the nickel in the reduction process, reduces the polymerization of the Pd at high temperature, and improves the dispersion degree of the main active component.

For hydrogenation reaction, generally, before the catalyst is applied, the hydrogenation catalyst needs to be reduced first to ensure that the active component exists in a metal state, so that the catalyst can have hydrogenation activity. Because activation is a high temperature calcination process during catalyst preparation, the metal salt decomposes to metal oxides, which form clusters, which are typically nano-sized. Different oxides need to be reduced at different temperatures due to different chemical properties. However, for nano-sized metals, a critical temperature is around 200 ℃, and above this temperature, the aggregation of metal particles is very significant. Therefore, the reduction temperature of the active component is very important for the hydrogenation catalyst.

The idea of the invention for solving the problem of catalyst coking is as follows:

the selective hydrogenation reaction of alkyne takes place in the main active center of the composition, such as Pd, rh, and the macromolecules such as green oil produced in the reaction, and easily enter the macropores of the catalyst. In the macropores of the catalyst, a Ni/Cu component is loaded, wherein Ni has a saturation hydrogenation function, and the green oil component can perform a saturation hydrogenation reaction at an active center consisting of Ni/Cu. Because the double bonds are saturated by hydrogenation, the green oil component can not generate polymerization reaction any more or the polymerization reaction rate is greatly reduced, the chain growth reaction is terminated or delayed, a fused ring compound with huge molecular weight 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 alloy to be positioned in the catalyst macropores is that Ni/Cu is loaded in the form of microemulsion, and the grain diameter of the microemulsion is larger than the pore diameter of carrier micropores and smaller than the maximum 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.

In the invention, cu and Ni are loaded together, so that the reduction temperature of Ni can be reduced, because NiO is required to be completely reduced independently, the reduction temperature is generally 450-500 ℃, pd agglomeration can be caused at the temperature, and after the Cu/Ni alloy is formed, the reduction temperature can be reduced by more than 100 ℃ and can reach 350 ℃ compared with the reduction temperature of pure Ni, so that the agglomeration of Pd in the reduction process is relieved.

In the invention, a small amount of Pd supported by 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 as low as 150 ℃.

In the invention, in the process of loading palladium by the solution method, the solution containing palladium enters the pores more quickly due to the siphonage action of the pores, the palladium exists in the form of chloropalladate ions, and the ions can form chemical bonds with hydroxyl on the surface of the carrier to target the palladium quickly, so that the faster the solution enters the pore channels, the faster the loading speed. Therefore, the catalyst is more easily supported in the pores during the impregnation of Pd by the solution method.

The catalyst adopted by the invention has the advantages of high activity,the carrier is required to have a bimodal pore distribution structure, particularly a large pore with the pore diameter of 70-300 nm, and a small pore with the pore diameter of 15-35 nm. The carrier is 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 above 80%, and the carrier may also contain other metal oxides such as magnesia, titania, etc.

The invention is not particularly limited in the process of loading Ni, cu and Pd in a microemulsion manner, and Ni, cu and Pd can be distributed in macropores of the carrier as long as the particle size of the microemulsion with the particle size of more than 35nm and less than 300nm 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.

In the present invention, the kind and addition amount of the oil phase, the surfactant and the co-surfactant are not particularly limited, and the kind and addition amount of the oil phase, the surfactant and the co-surfactant 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 the nonionic surfactant, and more preferably polyethylene glycol octyl phenyl ether or cetyl trimethyl ammonium bromide; the cosurfactant is an organic alcohol, preferably a C4-C6 alcohol, more preferably n-butanol and/or n-pentanol.

In the microemulsion, the recommended weight ratio of the water phase to the oil phase is 2.0-3.0, the weight ratio of the surfactant to the oil phase is 0.15-0.50, the weight ratio of the surfactant to the cosurfactant is 1.0-1.2, the grain diameter of the microemulsion is controlled to be larger than the pore diameter of a small pore of a carrier and smaller than the pore diameter of a large pore of the carrier, and the grain diameter of the microemulsion is controlled to be larger than 35nm and smaller than 300nm. The microemulsion has a particle size smaller than the pore size of the macropore, so that the loading of active components is facilitated, and the distribution of the active components, particularly Ni and Cu, in the prepared catalyst is more uniform. The grain diameter of the microemulsion is larger than the maximum aperture of the small hole and smaller than the minimum aperture of the large hole, which is more beneficial to the loading of the active component, and the distribution of the active component, especially Ni and Cu, in the prepared catalyst is more uniform.

The hydrogenation method is characterized in that in the preparation process of the catalyst, the sequence of the solution method load of Pd and the load of Ni/Cu is not limited, the step of loading Pd by microemulsion is after the step of loading Ni and Cu by microemulsion, and the step of loading Au by solution is after the step of loading Pd by solution.

The invention also provides a more specific catalyst, and a preparation method of the catalyst comprises the following steps:

(1) Dissolving precursor salt of Ni and Cu in water, adding metered oil phase, surfactant and cosurfactant, fully stirring to form microemulsion, controlling the particle size of the microemulsion to be more than 35nm and less than 300nm, adding the carrier into the prepared microemulsion, soaking for 0.5-4 hours, filtering out residual liquid, drying for 1-6 hours at 80-120 ℃, and roasting for 2-8 hours at 400-600 ℃. Obtaining a semi-finished product catalyst A;

(2) Dissolving Pd precursor salt in water, adjusting the pH value to 1.8-2.8, adding the semi-finished catalyst A into a 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) Loading Rh in a solution saturation impregnation method, namely preparing a Rh salt solution which is 80-110% of the saturated water absorption of a carrier, precipitating the Rh salt solution for 0.5-2 h after loading Rh on a semi-finished catalyst B, drying the semi-finished catalyst B at 100-120 ℃ for 1-4 h, and roasting the semi-finished catalyst B at 400-550 ℃ for 4-6 h to obtain a semi-finished catalyst C;

(4) Dissolving Pd precursor salt in water, adding metered oil phase, surfactant and cosurfactant, fully stirring to form microemulsion, controlling the particle size of the microemulsion to be more than 35nm and less than 300nm, adding the semi-finished catalyst C into the prepared microemulsion, soaking for 0.5-4 hours, filtering out residual liquid, drying for 1-6 hours at 80-120 ℃, and roasting for 2-8 hours at 400-600 ℃ to obtain the catalyst.

The carrier in the step (1) is alumina or mainly alumina and 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 above 80%, and the carrier may also contain other metal oxides such as magnesia, titania, etc.

The carrier in the step (1) can be spherical, cylindrical, clover-shaped and the like.

The precursor salts of Pd, rh, ni and Cu in the steps (1) and (3) are soluble salts, and can be nitrates, chlorides or other soluble salts.

The reduction temperature of the catalyst of the present invention is preferably 150 to 200 ℃.

The catalyst had the following characteristics: at the beginning of the hydrogenation reaction, the hydrogenation activity of palladium is high and is mainly distributed in the pores, so that the selective hydrogenation reaction of acetylene mainly occurs in the pores. 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 due to the larger molecular size, the substances enter the macropores more frequently and the retention time is longer, the hydrogenation reaction of double bonds can be generated under the action of the nickel catalyst, so that saturated hydrocarbon or aromatic hydrocarbon without isolated double bonds is generated, and substances with larger molecular weight are not generated any more.

The method of the invention has the main advantages that: (1) The invention adopts the fixed bed reactor, the reactor has simple structure, large production capacity, wide application, mature technology, convenient operation of catalyst filling, start-up and regeneration and small investment; (2) The catalyst prepared by using the carrier with bimodal pore distribution can greatly improve the hydrogenation activity and the anti-coking performance, and simultaneously, the addition of the selected auxiliary agent plays a synergistic role, so that the purposes of improving the hydrogenation activity and the stability of the catalyst are achieved, the service life of the catalyst is prolonged, and the long-term stable operation of the hydrogenation process is ensured.

The alkyne removing method can greatly reduce the reduction temperature of the catalyst to 150-200 ℃ at the lowest, and reduce the agglomeration of active components in the reduction process.

By using the alkyne removal method, even if the raw material contains more heavy fractions, the generation amount of green oil of the catalyst is greatly increased, and the activity and the selectivity of the catalyst still do not tend to be reduced.

Drawings

FIG. 1 is a graph showing the distribution of reduction temperature peaks of Ni/Cu.

FIG. 2 is a flow diagram of carbon three hydrogenation using a non-prehydrogenation process.

FIG. 3 is a carbon three hydrogenation flow diagram using a pre-hydrogenation process.

In the figure: 1-oil wash column; 2-water washing tower; 3, a heat exchanger; 4-alkaline washing tower; 5-a demethanizer; 6-deethanizer; 7-depropanizer; 8-carbon three hydrogenation reactor; 9-a front-end depropanizer; 10-a carbon hydrogenation reactor; 11-compressor.

Detailed Description

The following examples illustrate the invention in detail: the present example is carried out on the premise of the technical scheme of the present invention, and detailed embodiments and processes are given, but the scope of the present invention is not limited to the following examples, and the experimental methods without specific conditions noted in the following examples are generally performed according to conventional conditions.

The analysis and test method comprises the following steps:

comparison table: GB/T-5816;

pore volume: GB/T-5816;

the content of active components in the catalyst is as follows: atomic absorption method;

microemulsion particle size distribution of Ni/Cu alloy: a dynamic light scattering particle size analyzer, which is analyzed on an M286572 dynamic light scattering analyzer;

the conversion and selectivity in the examples were calculated according to the following formulas:

MAPD conversion (%) =100 × Δ MAPD/inlet MAPD content

Propylene selectivity (%) =100 ×. DELTA.propylene/. DELTA.MAPD

Example 1

Carrier: a commercially available spherical alumina carrier with bimodal pore distribution and a diameter of 4mm is adopted, and 100g of the spherical alumina carrier is weighed after being calcined at high temperature for 4 hours. The calcination temperature and the physical index of the carrier are shown in Table 1.

Preparing a catalyst:

(1) Weighing a certain amount of nickel nitrate, dissolving copper chloride in deionized water, adding a certain amount of cyclohexane, triton X-100 and n-butanol, fully stirring to form a microemulsion, soaking 100g of the weighed carrier into the prepared microemulsion for 1 hour, washing the microemulsion to be neutral by using the deionized water, drying the microemulsion for 2 hours at 120 ℃, and baking the microemulsion at 550 DEG C

And (5) burning for 5 hours. Obtaining a semi-finished product catalyst A.

(2) Weighing a certain amount of palladium nitrate, dissolving in deionized water, adjusting the pH value to 1, then dipping the semi-finished catalyst A into the prepared Pd salt solution, drying for 2 hours at 110 ℃ after dipping and adsorption for 1 hour, and roasting for 6 hours at 380 ℃ to obtain a semi-finished catalyst B.

(3) Weighing rhodium nitrate, preparing into a solution by using deionized water, adding a semi-finished catalyst B into the solution, shaking, drying for 3 hours at 110 ℃ after the solution is completely absorbed, and roasting for 4 hours at 500 ℃ 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 is mixed with N in a molar ratio ₂ :H ₂ The mixed gas of =1:1 is reduced for 12h at 350 ℃.

Example 2

Carrier: a commercially available spherical carrier with bimodal pore distribution and a diameter of 4mm is adopted, and the spherical carrier comprises 90% of alumina and 10% of titanium oxide. After high-temperature roasting for 4 hours, 100g of the carrier is weighed, and the physical indexes of the carrier are shown in table 1.

Preparing a catalyst:

(1) Weighing a certain mass of nickel nitrate, dissolving copper chloride in deionized water, adding a certain amount of cyclohexane, tritonX-100 and n-hexanol, and fully stirring to form microemulsion. The carrier is added into the prepared microemulsion for dipping for 1 hour, washed to be neutral by deionized water, dried for 2 hours at 120 ℃ and roasted for 5 hours at 550 ℃. Obtaining a semi-finished product catalyst A.

(2) Weighing a certain amount of palladium nitrate, dissolving the palladium nitrate in water, adding a certain amount of cyclohexane and TritonX-100, and fully stirring 6.03g of n-hexanol to form microemulsion. And adding the semi-finished catalyst A into the prepared microemulsion, soaking for 4 hours, washing to be neutral by using deionized water, drying for 4 hours at 90 ℃, and roasting for 2 hours at 600 ℃ to obtain a semi-finished catalyst B.

(3) Weighing a certain amount of palladium nitrate salt, dissolving in water, adjusting the pH value to 2, adding the semi-finished product B into a Pd salt solution, soaking and adsorbing for 1h, drying for 2h at 110 ℃, and roasting for 6h at 380 ℃ to obtain a semi-finished product catalyst C.

(4) Weighing a certain amount of rhodium nitrate, dissolving the rhodium nitrate into deionized water, soaking the semi-finished catalyst C into the prepared solution, drying the semi-finished catalyst C for 3 hours at 110 ℃, and roasting the semi-finished catalyst C for 4 hours at 500 ℃ to obtain the finished catalyst.

Before use, the mixture is placed in a fixed bed reaction device and is mixed with N ₂ :H ₂ The mixed gas of =1:1 is reduced for 12h at 170 ℃.

Example 3

Carrier: a commercially available spherical alumina carrier with bimodal pore distribution and a diameter of 4mm was used. After high-temperature roasting for 4 hours, 100g of the carrier is weighed, and the physical indexes are shown in table 1.

Preparing a catalyst:

(1) Weighing a certain amount of palladium nitrate salt, dissolving in water, adjusting the pH value to 2, adding the carrier into a Pd salt solution, soaking and adsorbing for 1h, drying for 2h at 110 ℃, and roasting for 6h at 380 ℃ to obtain a semi-finished catalyst A.

(2) Weighing a certain amount of rhodium nitrate, dissolving the rhodium nitrate into deionized water, soaking the semi-finished catalyst A into the prepared solution, drying the solution at 110 ℃ for 3 hours, and roasting the solution at 500 ℃ for 4 hours to obtain a semi-finished catalyst B.

(3) Weighing a certain amount of nickel nitrate and copper chloride, dissolving in water, adding a certain amount of cyclohexane and TritonX-100, and fully stirring 6.03g of n-hexanol to form microemulsion. Adding the semi-finished catalyst B into the prepared microemulsion, soaking for 4 hours, washing to be neutral by deionized water, drying for 4 hours at 90 ℃, and roasting for 2 hours at 600 ℃. Obtaining a semi-finished product catalyst C.

(4) Weighing a certain amount of palladium nitrate, dissolving the palladium nitrate in water, adding a certain amount of cyclohexane and TritonX-100, and fully stirring 6.03g of n-hexanol to form microemulsion. Adding the semi-finished catalyst C into the prepared microemulsion, soaking for 4 hours, washing to be neutral by deionized water, drying for 4 hours at 90 ℃, and roasting for 2 hours at 600 ℃. And obtaining the finished catalyst.

Before use, the mixture is placed in a fixed bed reaction device and is mixed with N ₂ :H ₂ The mixed gas of =1:1 is reduced for 12h at 160 ℃.

Example 4

The catalyst composition and preparation procedure were the same as in example 3, and the composition of the raw materials was evaluated as shown in Table 3.

Example 5

Example 6

Example 7

Carrier: a commercially available spherical alumina carrier with bimodal pore distribution and a diameter of 4mm is adopted. After high-temperature roasting for 4 hours, 100g of the carrier is weighed, and the physical indexes are shown in table 1.

Preparing a catalyst:

(1) Weighing a certain amount of nickel nitrate and copper chloride, dissolving in water, adding a certain amount of cyclohexane and TritonX-100, and fully stirring 6.03g of n-hexanol to form microemulsion. The carrier is added into the prepared microemulsion to be dipped for 4 hours, then is washed to be neutral by deionized water, is dried for 4 hours at 90 ℃, and is roasted for 2 hours at 600 ℃. Obtaining a semi-finished product catalyst A.

(2) Weighing a certain amount of palladium nitrate salt, dissolving in water, adjusting the pH value to 2, adding the semi-finished catalyst A into a Pd salt solution, soaking and adsorbing for 1h, drying for 2h at 110 ℃, and roasting for 6h at 380 ℃ to obtain a semi-finished catalyst B.

(3) Weighing a certain amount of rhodium nitrate, dissolving the rhodium nitrate in deionized water, soaking the semi-finished catalyst B in the prepared solution, drying the semi-finished catalyst B for 3 hours at 110 ℃, and roasting the semi-finished catalyst B for 4 hours at 500 ℃ to obtain a semi-finished catalyst C.

(4) Weighing a certain amount of palladium nitrate, dissolving the palladium nitrate in water, adding a certain amount of cyclohexane and Triton X-100, and fully stirring 6.03g of n-hexanol to form microemulsion. Adding the semi-finished catalyst C into the prepared microemulsion, soaking for 4 hours, washing to be neutral by deionized water, drying for 4 hours at 90 ℃, and roasting for 2 hours at 600 ℃. And obtaining the finished catalyst.

Before use, the mixture is placed in a fixed bed reaction device and is subjected to reduction treatment for 12H at the temperature of 170 ℃ by using mixed gas with the molar ratio of N2: H2= 1:1.

Example 8

Preparing a catalyst:

(1) Weighing a certain amount of nickel nitrate and copper chloride, dissolving in water, adding a certain amount of cyclohexane and TritonX-100, and fully stirring 6.03g of n-hexanol to form microemulsion. The carrier is added into the prepared microemulsion for dipping for 4 hours, then is washed to be neutral by deionized water, is dried for 4 hours at the temperature of 90 ℃, and is roasted for 2 hours at the temperature of 600 ℃. Obtaining a semi-finished product catalyst A.

(2) Weighing a certain amount of palladium nitrate, dissolving the palladium nitrate in water, adding a certain amount of cyclohexane and TritonX-100, and fully stirring 6.03g of n-hexanol to form microemulsion. Adding the semi-finished catalyst A into the prepared microemulsion, soaking for 4 hours, washing to be neutral by deionized water, drying for 4 hours at 90 ℃, and roasting for 2 hours at 600 ℃. Obtaining a semi-finished product catalyst B.

(3) Weighing a certain amount of palladium nitrate salt, dissolving in water, adjusting the pH value to 2, adding the semi-finished catalyst B into a Pd salt solution, soaking and adsorbing for 1h, drying for 2h at 110 ℃, and roasting for 6h at 380 ℃ to obtain a semi-finished catalyst C.

(4) Weighing a certain amount of rhodium nitrate, dissolving in deionized water, soaking 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.

Before use, the mixture is placed in a fixed bed reaction device and is subjected to reduction treatment for 12H at the temperature of 150 ℃ by using mixed gas with the molar ratio of N2: H2= 1:1.

Comparative example 1

Preparing a catalyst:

(1) Weighing a certain amount of nickel nitrate, dissolving the nickel nitrate in 70ml of deionized water, adding a certain amount of cyclohexane, triton X-100 and n-butanol, fully stirring to form a microemulsion, dipping the carrier into the prepared microemulsion, washing the carrier to be neutral by using the deionized water after dipping for 1 hour, drying the carrier for 2 hours at 120 ℃, and roasting the carrier for 5 hours at 550 ℃. Thus obtaining a semi-finished catalyst A1.

(2) Weighing a certain amount of palladium nitrate, dissolving in deionized water, adjusting the pH value to 1, then dipping the semi-finished catalyst A into the prepared Pd salt solution, drying for 2 hours at 110 ℃ after dipping and adsorption for 1 hour, and roasting for 6 hours at 380 ℃ to obtain a semi-finished catalyst B1.

(3) Weighing rhodium nitrate, preparing the rhodium nitrate into a solution by using deionized water, immersing the semi-finished catalyst B1 into the prepared solution, shaking, drying for 3 hours at 110 ℃ after the solution is completely absorbed, and roasting for 4 hours at 500 ℃ to obtain the required catalyst.

Before use, the mixture is placed in a fixed bed reaction device and is mixed with N in a molar ratio ₂ :H ₂ The mixed gas of 1:1, at 490 ℃, is subjected to reduction treatment for 12h.

Comparative example 2

Carrier: a commercially available spherical carrier with bimodal pore distribution and a diameter of 4mm is adopted, and the composition of the carrier is 90% of alumina and 10% of titanium oxide. After high-temperature roasting for 4 hours, 100g of the carrier is weighed, and the physical indexes are shown in table 1.

Preparing a catalyst:

(1) Weighing a certain amount of nickel nitrate, dissolving copper nitrate in deionized water, adding a certain amount of cyclohexane, 14.3g of Triton X-100 and 13.60g of n-hexanol, and fully stirring to form microemulsion. The carrier is added into the prepared microemulsion for dipping for 1 hour, washed to be neutral by deionized water, dried for 2 hours at 120 ℃ and roasted for 5 hours at 550 ℃. Thus obtaining a semi-finished catalyst A1.

(2) Weighing a certain amount of palladium nitrate salt, dissolving in water, adjusting the pH value to 2, adding the semi-finished catalyst A1 into a Pd salt solution, soaking and adsorbing for 1h, drying for 2h at 110 ℃, and roasting for 6h at 380 ℃ to obtain the finished catalyst.

Before use, the mixture is placed in a fixed bed reaction device and is mixed with N ₂ :H ₂ The mixed gas of =1:1 is reduced for 12h at 350 ℃.

Comparative example 3

Carrier: a commercially available spherical alumina support with monomodal pore distribution and a diameter of 4mm was used. After high-temperature roasting for 4 hours, 100g of the carrier is weighed, and the physical indexes are shown in table 1.

Preparing a catalyst:

(1) Weighing a certain amount of palladium chloride salt, dissolving in water, adjusting the pH value to 3, adding the weighed carrier into a Pd salt solution, soaking and adsorbing for 2h, drying for 1h at 120 ℃, and roasting for 4h at 450 ℃ to obtain a semi-finished catalyst A1.

(2) Weighing a certain amount of rhodium nitrate, dissolving the rhodium nitrate in deionized water, soaking the semi-finished catalyst A1 in the prepared solution, drying the solution for 4 hours at 100 ℃ after the solution is completely absorbed, and roasting the solution for 6 hours at 400 ℃ to obtain the required catalyst.

The contents of the components in the catalyst are shown in Table 2.

Use ofPlacing the mixture in a fixed bed reaction device in a molar ratio of N ₂ :H ₂ The mixed gas of 1:1, at 350 ℃, is subjected to reduction treatment for 12h.

Comparative example 4

Carrier: a commercially available spherical alumina carrier with bimodal pore distribution and a diameter of 4mm was used. After high-temperature roasting for 4 hours, 100g of the carrier is weighed, and the physical property indexes are shown in table 1.

Preparing a catalyst:

(2) Weighing a certain amount of rhodium nitrate, 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 a semi-finished catalyst B.

(3) Weighing a certain amount of nickel nitrate, dissolving ferric chloride in water, adding a certain amount of cyclohexane and TritonX-100, and fully stirring 6.03g of n-hexanol to form microemulsion. Adding the semi-finished catalyst B into the prepared microemulsion, soaking for 4 hours, washing to be neutral by deionized water, drying for 4 hours at 90 ℃, and roasting for 2 hours at 600 ℃. And obtaining the finished catalyst.

TABLE 1 Carrier Properties in examples and comparative examples

TABLE 2 content of active components of catalysts in examples and comparative examples

The performance of the catalyst is evaluated in a fixed bed single-stage reactor. The loading of the catalyst is 50ml, the space velocity of the reaction materials is 60/h, the operating pressure is 2.5MPa, and the hydrogen/PDMA is 1.2. The reaction mass composition is shown in Table 3.

TABLE 3 reaction Material composition (volume content composition)

	C ₂	C ₃ H ₈	C ₃ H ₆	MAPD	C ₄
						Examples 1 to 3	0.3	7.4	88.5	3.5	0.3
Example 4	0.2	7.6	90.0	2.0	0.2
						Example 5	0.2	8.0	90.6	1.0	0.2
Example 6	0.2	5.8	93.6	0.3	0.1
						Example 7	0.2	6.5	92.9	0.3	0.1
Example 8	0.3	7.5	88.4	3.5	0.3
						Comparative examples 1 to 4	0.3	7.4	88.5	3.5	0.3

The evaluation conditions of the catalyst are shown in Table 4.

TABLE 4 evaluation conditions of catalysts

TABLE 5 catalyst evaluation results

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

1. An alkyne removing method for a carbon three-fraction selective hydrogenation process is characterized in that after hydrogen is prepared for the carbon three-fraction serving as a hydrogenation raw material, propyne and allene in the material are converted into propylene in a reactor; selecting the hydrogenation reaction conditions: the inlet temperature of the reactor is 30-50 ℃, the reaction pressure is 1.5-3.5 MPa, and the liquid phase space velocity is 15-120 h ^-1 The molar ratio of hydrogen to MAPD is = 1-10; the catalyst carrier is alumina or mainly alumina and has a bimodal pore distribution structure, the pore diameter of a small pore is 15-35 nm, the pore diameter of a large pore is 70-300 nm, and the specific surface area of the catalyst is 20-50 m ² The catalyst at least contains Pd, rh, ni and Cu, the load of the Pd is loaded by solution load or two forms of solution and microemulsion, the Ni and Cu are loaded in a microemulsion mode, the mass of the catalyst is 100 percent, the content of the Ni is 5.0 to 10 percent, the weight ratio of the Cu to the Ni is 0.1 to 1.0, the content of the solution loaded Pd is 0.25 to 0.40 percent, the weight ratio of the Rh to the solution loaded Pd is 1.5 to 6.0, the content of the microemulsion loaded Pd is 1/100 to 1/200 of the content of Ni and Cu, and the microemulsion loaded Ni, cu and Pd are mainly distributed in macropores of the carrier; the reduction temperature of the catalyst is 150-200 ℃.

2. The alkyne removal method of claim 1, wherein the selective hydrogenation reaction conditions are: the inlet temperature of the adiabatic bed reactor is 30-50 ℃, the reaction pressure is 2-3 MPa, and the liquid phase space velocity is 30-60 h ^-1 The molar ratio of hydrogen to MAPD is 1.1-3.0.

3. The alkyne removal method of claim 1, wherein the content of Ni is 6.8-8.0%, the weight ratio of Cu to Ni is 0.4-0.8, and the microemulsion-supported Pd content is 1/120-1/150 of the Ni + Cu content, based on 100% by mass of the catalyst.

4. The alkyne removal process of claim 1, wherein the reactor is a single-stage adiabatic bed.

5. The alkyne removal method according to claim 1, wherein the hydrogenation raw material is from a sequential separation process, and the volume ratio of the materials is as follows: 70 to 90 percent of propylene, 5 to 30 percent of propane, 2.0 to 5.0 percent of propine and propadiene; or the hydrogenation raw material comes from a front-end depropanization front-end hydrogenation process, and the volume ratio of the materials is as follows: 80 to 95 percent of propylene, 5 to 20 percent of propane and 0.2 to 2.5 percent of propine and propadiene.

6. A process according to claim 1, wherein the catalyst support used is alumina or essentially alumina, al ₂ O ₃ The crystal form is alpha, theta or a mixed crystal form thereof, the content of alumina in the catalyst carrier is more than 80%, and the carrier can also contain other metal oxides, wherein the other metal oxides are magnesium oxide and titanium oxide.

7. The alkyne-removing method as claimed in claim 1, wherein the solution loading of Pd and Rh is carried out by saturation impregnation during the preparation of the catalyst.

8. The alkyne removal method as claimed in claim 1, wherein the microemulsion 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.

9. The method of removing alkynes according to claim 8, wherein the oil phase is a C6-C8 saturated alkane or cycloalkane; the surfactant is an ionic surfactant and/or a nonionic surfactant; the cosurfactant is C4-C6 alcohol.

10. The method of claim 9, wherein the oil phase is cyclohexane, n-hexane; the nonionic surfactant is polyethylene glycol octyl phenyl ether or hexadecyl trimethyl ammonium bromide; the cosurfactant is n-butanol and/or n-pentanol.

11. The method of claim 8, wherein the microemulsion has a weight ratio of surfactant to co-surfactant of 1.0 to 1.2, a weight ratio of aqueous phase to oil phase of 2.0 to 3.0, and a weight ratio of surfactant to oil phase of 0.15 to 0.50.

12. The alkyne removal method as recited in claim 9, wherein the preparation process 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, fully stirring to form a microemulsion, controlling the particle size of the microemulsion to be more than 35nm and less than 300nm, and preparing the microemulsion under the conditions that: adding an oil phase, a surfactant and a cosurfactant, wherein the weight ratio of the surfactant to the cosurfactant is 1.0-1.2, the weight ratio of the water phase to the oil phase is 2.0-3.0, and the weight ratio of the surfactant to the oil phase is 0.15-0.50; adding the carrier into the prepared microemulsion, dipping 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 A;

(2) Dissolving Pd precursor salt in water, adjusting the pH value to 1.5-2.5, adding the semi-finished catalyst A into a 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) Loading Rh in a saturated dipping method, namely preparing a Rh salt solution which is 80-110% of the saturated water absorption of a carrier, adjusting the pH value to 1-5, and roasting the semi-finished catalyst B at 500-550 ℃ for 4-6 hours after loading Rh 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 more than 35nm and less than 300nm, and preparing the microemulsion under the conditions that: adding oil phase, surfactant and cosurfactant in the weight ratio of 1.0-1.2 to 2.0-3.0, and surfactant and oil phase in the weight ratio of 0.15-0.50, soaking the semi-finished catalyst C in the prepared microemulsion for 0.5-4 hr, filtering to eliminate residual liquid, drying at 60-120 deg.c for 1-6 hr, and roasting at 300-600 deg.c for 2-8 hr to obtain the required catalyst.