WO2017201644A1 - 一种钯系负载型加氢催化剂及其制备方法与应用 - Google Patents

一种钯系负载型加氢催化剂及其制备方法与应用 Download PDF

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WO2017201644A1
WO2017201644A1 PCT/CN2016/082976 CN2016082976W WO2017201644A1 WO 2017201644 A1 WO2017201644 A1 WO 2017201644A1 CN 2016082976 W CN2016082976 W CN 2016082976W WO 2017201644 A1 WO2017201644 A1 WO 2017201644A1
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catalyst
palladium
hours
carrier
bipyridine
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French (fr)
Inventor
车春霞
梁玉龙
钱颖
韩伟
张峰
苟尕莲
景喜林
常晓昕
桂强
谷丽芬
颉伟
张忠东
黄德华
谭都平
高源�
程琳
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Petrochina Co Ltd
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Petrochina Co Ltd
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Priority to PCT/CN2016/082976 priority Critical patent/WO2017201644A1/zh
Priority to KR1020187034998A priority patent/KR102156606B1/ko
Priority to JP2018533766A priority patent/JP6636162B2/ja
Priority to DE112016006477.2T priority patent/DE112016006477T5/de
Publication of WO2017201644A1 publication Critical patent/WO2017201644A1/zh
Priority to US16/010,005 priority patent/US10800717B2/en
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Definitions

  • the invention relates to the technical field of hydrogenation catalysts, in particular to a palladium-based supported hydrogenation catalyst and a preparation method and application thereof.
  • Ethylene is one of the most important basic raw materials in the petrochemical industry. As a monomer for the synthesis of various polymers, it is generally produced by steam cracking of petroleum hydrocarbons such as ethane, propane, butane, naphtha and light diesel. Got it. The ethylene-based C2 fraction obtained by this method also contains 0.5% to 2.5% (molar fraction) of acetylene. The presence of acetylene complicates the polymerization of ethylene and can degrade polymer properties. When polyethylene is produced by high pressure method, there is a risk of explosion due to the accumulation of acetylene.
  • the presence of acetylene also reduces the activity of the polymerization catalyst and increases the consumption of the catalyst; therefore, the acetylene in ethylene must be It can be used as a monomer for synthetic polymers by dropping below a certain value. Therefore, the C2 fraction, which is the main product of the ethylene industry, needs to be purified by hydrogenation and deacetylation to be used as a production material for polymerization grades for the production of downstream products such as polyethylene.
  • the process of catalytic selective hydrogenation is generally divided into a pre-hydrogenation process and a post-hydrogenation process.
  • the pre-hydrogenation process and the post-hydrogenation process are mainly based on the difference in the position of the hydrogenation reactor.
  • the hydrogenation reactor is called the pre-hydrogenation process before the demethanizer, and the hydrogenation reactor is located after the demethanizer. It is called post hydrogenation process.
  • the post-hydrogenation process is mainly represented by the hydrogenation process developed by ABB Lummus Global of the United States.
  • the sequential separation process is adopted, that is, the methane and ethane are sequentially removed, and then the C2 fraction is hydrogenated to remove acetylene.
  • the hydrogenation process is more common in ethylene production systems introduced earlier in the country.
  • the pre-hydrogenation process is divided into two processes: pre-de-ethanation pre-hydrogenation and pre-de-propane pre-hydrogenation, respectively, by Linde Group of Germany and Stone & Webster Engineering Corporation. Development, the hydrogenation reactor of the pre-depropanation pre-hydrogenation process is set before the demethanizer degassing tower, and the hydrogenation reactor of the pre-de-ethanation pre-hydrogenation process is set before the deethanizer tower .
  • the alkyne and diene contained in the C2 and C3 fractions are usually removed by selective hydrogenation, and the selective hydrogenation catalyst is obtained by supporting a noble metal such as palladium on a porous inorganic material carrier (for example, US4762956) Introduced in the).
  • US4404124 prepares a selective hydrogenation catalyst with active component shell by step impregnation method, which can be applied to the selective hydrogenation of C2 and C3 fractions to eliminate propane and propylene in ethylene and propylene in ethylene. Alkene.
  • US5587348 uses alumina as a carrier to prepare an excellent acetylene hydrogenation catalyst by complexing silver with palladium and adding alkali metal fluoride; the catalyst has the effect of reducing green oil production, increasing ethylene selectivity and reducing oxygenate formation. The characteristics of the volume.
  • U.S. Patent No. 5,519,566 discloses a method for the preparation of a silver and palladium catalyst by wet reduction. A two-component selective hydrogenation catalyst of silver and palladium is prepared by adding an organic or inorganic reducing agent to the impregnation solution.
  • the above conventional selective hydrogenation catalysts are prepared by impregnation method, and the active components thereof are all Pd and Ag bimetals. These methods have the following disadvantages: (1) Due to the pore structure of the carrier, the dispersion of the active component cannot be precisely controlled, and the randomness is strong; (2) The surface tension of the immersion liquid, the effect of solvation, the precursor of the metal active component The body is deposited on the surface of the carrier in the form of aggregates, which cannot form a uniform distribution. (3) The hydrogenation of the C2 fraction has higher selectivity to the catalyst, and the interaction between the active component Ag and the main active component Pd is to improve the selectivity of the catalyst.
  • the catalyst prepared by the traditional method due to the different surface tension of the palladium salt solution and the silver salt solution, the Pd and Ag can not form the same layer distribution on the carrier, and the additive effect of Ag is not obvious, and it is necessary to increase the Ag.
  • the amount is used to promote the action of the auxiliary agent, thereby causing the transfer of hydrogen to be hindered, and the possibility of occurrence of the oligomerization reaction is increased, so that the amount of green oil generated increases, which affects the life of the catalyst.
  • the occurrence of the above three problems easily leads to poor dispersibility of the metal active component, and low selectivity of the reaction, thereby affecting the performance of the catalyst.
  • US4714692 uses a microemulsion method to prepare a single component precious metal catalyst.
  • a multi-component catalyst is prepared by this method, the influence of the solvation effect on the distribution of the active component of the catalyst is still not avoided.
  • Both CN102206130A and CN102205243A form a polymer chain coating on the surface of the carrier by adsorbing a specific polymer compound on the carrier, and reacting the compound having a specific functional group with the polymer chain on the carrier to enable The functional group complexed by the active component undergoes a complexation reaction on the surface functional groups of the carrier by the active component to ensure order and high dispersion of the active component.
  • the carrier adsorbs a specific polymer compound by chemical adsorption of the hydroxyl group of the carrier alumina and the polymer compound, and the amount of the polymer compound adsorbed by the carrier will be limited by the amount of the hydroxyl group of the alumina;
  • the complexation of polymer chains with palladium ions is not strong, sometimes the loading of active components is not required, and some active components remain in the impregnation solution, resulting in an increase in catalyst cost; and the preparation of C2 fractions by these two methods Hydrogenation catalysts also have the disadvantage of complicated process flow.
  • CN104971698A discloses an alumina shaped article comprising R 1 R 2 R 3 N + X - and a preparation method and application thereof, wherein said R 1 R 2 R 3 N + X - is selected from the group consisting of primary amine salts and secondary ammonium salts One or more of a salt, a tertiary ammonium salt, and a quaternary ammonium salt, X is selected from chlorine, bromine or iodine, and the substituent may be a linear or branched alkyl group, a cycloalkyl group or an aryl group, or may be A hydrocarbon group having a hydroxyl group and/or a heterocyclic substituent.
  • the alumina shaped product is prepared by molding and drying the alumina-containing support, placing it in an autoclave, and heat-treating at room temperature to 250 ° C with an appropriate amount of R 1 R 2 R 3 N + X - solution, after cooling.
  • the mixture was dried at 40 ° C to 250 ° C to remove excess solvent, and an alumina carrier having a large specific surface area and a large pore volume of R 1 R 2 R 3 N + X - was obtained.
  • the carrier is particularly suitable for the preparation of a Mo-Ni-based supported hydrogenation catalyst for hydrogenation of gasoline and diesel oil, and contributes to an increase in the hydrodesulfurization activity of the catalyst.
  • the organic matter used in the method contains chlorine, bromine or iodine, it is easy to form strong acid centers Cl - , Br - and I - on the surface of the catalyst after activation, resulting in unsaturated olefins and alkynes.
  • the polymerization of diolefins leads to the mass production of “green oil”, and the catalyst coking is greatly increased, which affects the service life of the catalyst.
  • the carrier prepared by the method is a carrier with large specific surface area and large pore volume, and is not suitable for preparing Pd system with shell distribution. catalyst.
  • an object of the present invention is to provide a palladium-based supported hydrogenation catalyst which is more excellent in performance, a preparation method and application thereof.
  • the catalyst preparation method provided by the invention enables the palladium atom and another metal atom to be highly uniformly dispersed on the carrier, and can overcome the adverse effect of the surface tension of the impregnation liquid and the solvation effect on the dispersibility of the active component.
  • the present invention first provides a method for preparing a palladium-based supported hydrogenation catalyst, which comprises the steps of impregnating a carrier containing Al 2 O 3 with an organic solution containing a bipyridine derivative having a hydroxyl group. Optionally, it is dried and then impregnated with a mixed solution containing a main active component palladium ion (ie, a divalent palladium cation) and a co-active component Mn + ion, wherein M is selected from one of Ag, Au, Ni, Pb, and Cu. And optionally drying, and calcining to obtain the palladium-based supported hydrogenation catalyst.
  • a main active component palladium ion ie, a divalent palladium cation
  • Mn + ion co-active component
  • the bipyridine derivative having a hydroxyl group forms a strong adsorption with the carrier containing Al 2 O 3 , and then forms an organic complex with the metal cation of the main active component Pd and the co-active component M, Finally, a Pd-M supported catalyst in which the active component is highly dispersed is obtained.
  • the preparation method of the palladium-based supported hydrogenation catalyst of the present invention comprises the following steps:
  • the hydroxy-bipyridine/Al 2 O 3 precursor is impregnated with a mixed solution containing palladium ions and Mn + ions, optionally dried (ie, dried or not dried) to form ( Pd-M)-hydroxy-bipyridine/Al 2 O 3 precursor;
  • the carrier containing Al 2 O 3 is impregnated with an organic solution containing a bipyridine derivative having a hydroxyl group (that is, the above step (1)) is carried out at 20 ° C to 60 ° C, and impregnated.
  • the time is 2 to 24 hours.
  • the subsequent drying temperature may be from 60 ° C to 150 ° C and the time may be from 2 to 10 hours.
  • the hydroxy-bipyridine/Al 2 O 3 precursor (that is, the above step (2)) is impregnated with a mixed solution containing palladium ions and Mn + ions at 20 ° C to 100 ° C (preferably) It is carried out at 30 ° C to 100 ° C), and the immersion time is 2 to 24 hours.
  • the subsequent drying temperature may be from 60 ° C to 150 ° C and the time may be from 2 to 10 hours.
  • the calcination (i.e., the above step (3)) is carried out at a temperature of from 300 ° C to 600 ° C for a period of from 2 to 12 hours. More preferably, the calcination temperature is from 350 ° C to 600 ° C. Further, the baking is preferably carried out in an oxygen-containing atmosphere.
  • the carrier containing Al 2 O 3 used includes alumina and/or a mixture containing alumina and other oxides, and the like.
  • the other oxide may include one or a combination of silicon oxide, titanium oxide, magnesium oxide and calcium oxide.
  • the crystal form of Al 2 O 3 in the carrier may be a mixed crystal form of several of these crystal forms of ⁇ , ⁇ , ⁇ , ⁇ or more, preferably ⁇ , ⁇ or a mixed crystal form thereof.
  • the carrier containing Al 2 O 3 used may be spherical, spheroidal, cylindrical, toroidal, strip, clover or clover, or the like.
  • the hydroxyl group-containing bipyridine derivative comprises a hydroxyl group-containing 2,2'-bipyridine derivative and/or a hydroxyl group-containing 3,3'-bipyridine derivative, more preferably It is a 2,2'-bipyridine derivative having a hydroxyl group.
  • the solvent in the organic solution containing the bipyridine derivative having a hydroxyl group may be an organic solvent commonly used in the art, such as ethanol and/or diethyl ether.
  • the role of the solvent is to enable complete dissolution of the hydroxyl-containing bipyridine derivative, which facilitates its adsorption onto a carrier.
  • the amount of the solvent to be used is not particularly limited as long as the hydroxyl group-containing bipyridine derivative can be completely dissolved.
  • the molar ratio of the hydroxyl group-containing bipyridine derivative to the Pd and M in the mixed solution containing palladium ions and Mn + ions is from 1 to 100:1; more preferably The molar ratio is from 5 to 80:1; most preferably, the molar ratio is from 20 to 60:1.
  • the mixed solution containing palladium ions and Mn + ions may be a mixed solution of one or several soluble salts of palladium and one or several soluble salts of M.
  • it may be a mixed solution of Pd(NO 3 ) 2 and M(NO 3 ) n .
  • the amount of the palladium salt and the M salt in the mixed solution is determined depending on the content of Pd and M required in the catalyst; preferably, when M is Ag, the molar ratio of Ag to Pd in the mixed solution is 0.4 to 10: 1; when M is Au, the molar ratio of Au to Pd in the mixed solution is 0.5 to 15:1; when M is Ni, the molar ratio of Ni to Pd in the mixed solution is 0.4 to 20:1; In the case of Pb, the molar ratio of Pb to Pd in the mixed solution is from 1 to 10:1; when M is Cu, the molar ratio of Cu to Pd in the mixed solution is from 1 to 10:1.
  • the mixed solution containing palladium ions and Mn + ions has a pH of 1.5 to 4.0, more preferably 2.0 to 4.0.
  • the pH of the mixed solution can be adjusted using a conventional pH adjusting agent.
  • the preparation method of the palladium-supported hydrogenation catalyst may include the following steps:
  • the carrier containing Al 2 O 3 is impregnated with an organic solution containing a bipyridine derivative having a hydroxyl group, and reacted at 20 ° C to 60 ° C for 2 to 24 hours, and then the reaction product is optionally dried at 60 ° C to 150 ° C for 2 to 2 10 hours, a hydroxy-bipyridine/Al 2 O 3 precursor is obtained; wherein, preferably, the volume of the organic solution containing the hydroxyl group-containing bipyridine derivative is 80% of the volume of the Al 2 O 3 -containing carrier More than % (including 80%);
  • the hydroxy-bipyridine/Al 2 O 3 precursor prepared in the step (1) is impregnated with a mixed solution of palladium ions and Mn + ions having a pH of 1.5 to 4.0, and reacted at 30 ° C to 100 ° C for 2 to 24 hours.
  • reaction product is optionally dried at 60 ° C to 150 ° C for 2 to 10 hours to obtain a (Pd-M)-hydroxy-bipyridine/Al 2 O 3 precursor (in which hydroxy-bipyridine and (Pd+M) a molar ratio of from 1 to 100:1, preferably from 5 to 80:1, more preferably from 20 to 60:1); wherein, preferably, the volume of the mixed solution is the hydroxy-bipyridine/Al 2 60% to 200% of the volume of the O 3 precursor;
  • the (Pd-M)-hydroxy-bipyridine/Al 2 O 3 precursor prepared in the step (2) is calcined at 300 to 600 ° C for 2 to 12 hours to obtain the palladium-based supported hydrogenation catalyst.
  • the method for preparing the palladium-based supported hydrogenation catalyst further comprises the steps of: reducing the treatment with a hydrogen-containing gas before using the palladium-supported hydrogenation catalyst; A reduced state palladium-based supported hydrogenation catalyst was obtained.
  • the Al-O bond in the carrier containing Al 2 O 3 strongly adsorbs a hydroxyl group in the bipyridine derivative having a hydroxyl group, and the bipyridine derivative having a hydroxyl group is loaded to On the support, a precursor loaded with a functionalized molecular chain is obtained.
  • the remaining hydroxyl group derived from the hydroxybipyridine (that is, the hydroxyl group remaining after adsorption with the Al-O bond) and/or the nitrogen group in the precursor is complexed with the palladium ion and the Mn + ion to make the palladium ion and the M
  • the n+ ion is bound to a molecular chain adsorbed on the carrier, and the complexation reaction is an in-situ chemical reaction of the complex-metal ion, and the metal ion is bonded to the molecular chain through a chemical reaction instead of physical adsorption, so Pd, M
  • the atoms are uniformly distributed in the molecular chain, and the number of Pd atoms and M atoms bound on the molecular chain is proportional to the number of hydroxyl groups on the molecular chain and the number of nitrogen groups.
  • the Pd atom and the M atom are oxidized in situ to form a Pd
  • the preparation method provided by the invention mainly has the following advantages: First, since the Al-O bond in the carrier containing Al 2 O 3 strongly adsorbs the hydroxyl group in the bipyridine derivative having a hydroxyl group, the carrier can be effectively ensured The adsorption amount of pyridine avoids the loss of hydroxybipyridine in the solution; in addition, since the hydroxyl group and the nitrogen group of the hydroxybipyridine adsorbed on the carrier have strong complexing ability with the main active component Pd and the auxiliary active component M, It is ensured that the palladium ion and the Mn + ion in the solution react completely, avoid the loss of the active components Pd and M in the solution, reduce the production cost, and enable the metal atom to be highly uniformly dispersed on the carrier; meanwhile, the preparation method overcomes the immersion liquid The surface tension and solvation effects adversely affect the dispersion of Pd and M on the support.
  • the catalyst prepared by the preparation method of the present invention has excellent hydrogenation activity,
  • the present invention provides a palladium-based supported hydrogenation catalyst which is produced by the above-described preparation method of a palladium-based supported hydrogenation catalyst.
  • the catalyst has excellent activity, selectivity and anti-coking properties.
  • the content of Pd in the catalyst is 0.01% to 0.8% based on 100% by mass of the palladium-based supported hydrogenation catalyst; and when M is Ag, the content is 0.03% to 3%, when M is Au, the content is 0.02 to 0.25%, when M is Ni, the content is 0.04 to 3%, and when M is Pb, the content is 0.04 to 3%, when M When it is Cu, its content is 0.02 to 1%.
  • the palladium-based supported hydrogenation catalyst has a specific surface area of from 1 to 200 m 2 /g, a pore volume of from 0.15 to 0.8 mL/g, and a bulk density of from 0.5 to 1.2 g/cm. 3 .
  • the present invention provides the use of the above palladium-based supported hydrogenation catalyst in a acetylene selective hydrogenation process.
  • the acetylene selective hydrogenation process is a selective hydrogenation process of trace acetylene.
  • the acetylene selective hydrogenation process comprises a pre-depropanation hydrogenation process before the carbon distillate, a pre-dehydrogenation process before the carbon distillate, a hydrogenation process after the carbon distillate, and an ethylene refining process.
  • the catalyst preparation method provided by the invention makes the Pd atom and the M atom highly uniformly dispersed on the carrier, and overcomes the adverse effect of the surface tension of the impregnation liquid and the solvation effect on the dispersibility of the active component.
  • the palladium-based supported hydrogenation catalyst provided by the invention has excellent hydrogenation activity, ethylene selectivity and anti-coking property, and can be used for catalyzing selective hydrogenation of trace acetylene.
  • 1 is a flow chart of a carbon distillate post hydrogenation process using a sequential separation process
  • FIG. 2 is a flow chart of a hydrogenation process before de-ethane removal of a carbon distillate
  • FIG. 3 is a flow chart of a pre-de-propane hydrogenation process before carbon distillate
  • Figure 4 is a flow chart of an ethylene refining process using a sequential separation process
  • FIG. 5 is a flow chart of an ethylene refining process using a pre-de-ethane pre-hydrogenation process
  • FIG. 6 is a flow chart of a methanol to olefin (MTO) process employing a sequential separation process
  • FIG. 7 is a flow chart of an ethylene refining process using a pre-depropanation pre-hydrogenation process
  • FIG. 8 is a flow chart of a methanol to olefin (MTO) process using a pre-depropanation pre-hydrogenation process
  • 1 oil washing tower
  • 2 water washing tower
  • 3 alkaline washing tower
  • 4-dryer 5-demethanizer, 6-deethanizer, 7-carbon dihydrogenation reactor
  • 8-compressor 9 - ethylene rectification column
  • 10-ethylene refining reactor 11-depropanizer column
  • 12-propene rectification column 13-methanol ethylene reactor
  • 14-regenerator 15-separator
  • 16-methanol dehydration system Methyl ether reactor 17-methanol propylene reactor
  • 18-pre-cooling separator 19-quick separator
  • 20-four-stage compressor 21-four-stage separator.
  • the content of Pd, Ag, Au, Ni, Cu or Pb in the catalyst using a plasma emission spectrometer or an atomic absorption spectrometer (according to the standard GB/T 1537-94);
  • Ethylene selectivity (molar percentage of ethylene after reaction - mole percent of ethylene before reaction) / (molar percentage of acetylene before reaction - mole percent of acetylene after reaction).
  • a spherical ⁇ -Al 2 O 3 carrier (500 g) having a diameter of 3.5 mm, a specific surface area of 20.0 m 2 /g, a pore volume of 0.48 mL/g, and a bulk density of 0.82 g/cm 3 was weighed.
  • the pore size of the carrier is bimodal, and the pore diameter is 20 to 50 nm and 300 to 500 nm, respectively.
  • the above (Pd-Ag)/Al 2 O 3 catalyst was placed in a fixed bed reactor, and the catalyst was subjected to reduction treatment at 120 ° C for 3 hours with a purity of 99.9% of hydrogen at a space velocity of 200 h -1 .
  • the content of Pd in the catalyst S-1 was measured to be 0.03 wt.%, and the content of Ag was 0.10 wt.%.
  • a spherical ⁇ -Al 2 O 3 carrier (500 g) having a diameter of 3.5 mm, a specific surface area of 20.0 m 2 /g, a pore volume of 0.48 mL/g, and a bulk density of 0.82 g/cm 3 was weighed.
  • the pore size of the carrier is bimodal, and the pore diameter is 20 to 50 nm and 300 to 500 nm, respectively.
  • PVC polyvinyl chloride
  • THF tetrahydrofuran
  • the above (Pd-Ag)/Al 2 O 3 catalyst was placed in a fixed bed reactor, and the catalyst was subjected to reduction treatment at 120 ° C for 3 hours with a purity of 99.9% of hydrogen at a space velocity of 200 h -1 .
  • the content of Pd in the catalyst D-1 was measured to be 0.03 wt.%, and the content of Ag was 0.10 wt.%.
  • Example 1 The catalysts prepared in Example 1 and Comparative Example 1 were respectively used in a carbon distillate post-hydrogenation process using a sequential separation process.
  • the process flow diagram is shown in FIG. 1 , and the carbon distillate obtained by steam cracking petroleum hydrocarbons is sequentially After being treated by the oil washing tower 1, the water washing tower 2, the alkali washing tower 3, the dryer 4, the demethanizer 5, and the deethanizer 6, the carbon dihydrogenation reactor 7 is further subjected to selective hydrogenation for removal.
  • the two carbon dihydrogenation reactors are used in series to carry out the reaction, that is, the outlet materials of one reactor enter the two-stage reactor; each reactor has an independent gas distribution system; both reactors are fixed bed adiabatic reactors.
  • composition of the carbon two materials entering the carbon dihydrogenation reactor was: C 2 H 2 1.58%, C 2 H 4 81.55%, and C 2 H 6 16.87% (by volume percent).
  • SAN polystyrene acrylonitrile
  • DMF dimethylformamide
  • the above SAN/Al 2 O 3 precursor was added to 1000 mL of deionized water, and then 57.6 g of ethylenediamine was added. After stirring until completely dissolved, the reaction was refluxed for 1 hour. After cooling to room temperature, the solid reaction product was washed with deionized water. Neutral, then dried at 80 ° C for 5 hours to give a functionalized SAN/Al 2 O 3 precursor.
  • the above (Pd-Au)-SAN/Al 2 O 3 precursor was calcined at 380 ° C for 2 hours in an air atmosphere to obtain (Pd-Au) / Al 2 O 3 catalyst D-2.
  • the content of Pd in the catalyst D-2 was measured to be 0.045 wt.%, and the content of Au was 0.20 wt.%.
  • Example 2 The catalysts prepared in Example 2 and Comparative Example 2 were respectively used in a carbon distillate post hydrogenation process using a sequential separation process, and the process flow diagram is shown in FIG.
  • the two carbon dihydrogenation reactors are used in series to carry out the reaction, that is, the outlet materials of one reactor enter the two-stage reactor; each reactor has an independent gas distribution system; both reactors are fixed bed adiabatic reactors.
  • composition of the carbon two materials entering the carbon dihydrogenation reactor was: C 2 H 2 1.7%, C 2 H 4 74.3%, and C 2 H 6 24.0% (by volume percent).
  • a cylindrical carrier of ⁇ 4.5 mm, height 4.5 mm, specific surface area of 17 m 2 /g, and pore volume of 0.33 mL/g was weighed and contained 400 g of ⁇ -Al 2 O 3 and 100 g of magnesium oxide.
  • the above (Pd-Ni)/Al 2 O 3 catalyst was placed in a fixed bed reactor, and the catalyst was subjected to reduction treatment at 120 ° C for 3 hours with a purity of 99.9% of hydrogen at a space velocity of 200 h -1 .
  • the content of Pd in the catalyst S-3 was measured to be 0.056 wt.%, and the content of Ni was 0.098 wt.%.
  • a cylindrical carrier of ⁇ 4.5 mm, height 4.5 mm, specific surface area of 17 m 2 /g, and pore volume of 0.33 mL/g was weighed and contained 400 g of ⁇ -Al 2 O 3 and 100 g of magnesium oxide.
  • PVC polyvinyl chloride
  • THF tetrahydrofuran
  • the above (Pd-Ni)/Al 2 O 3 catalyst was placed in a fixed bed reactor, and the catalyst was subjected to reduction treatment at 120 ° C for 3 hours with a purity of 99.9% of hydrogen at a space velocity of 200 h -1 .
  • the content of Pd in the catalyst D-3 was measured to be 0.056 wt.%, and the content of Ni was 0.098 wt.%.
  • Example 3 and Comparative Example 3 were respectively used in the pre-de-ethane dehydrogenation process before the carbon distillate.
  • the process flow chart is shown in FIG. 2, and the carbon distillate obtained by steam cracking of petroleum hydrocarbons was sequentially passed.
  • the oil washing tower 1, the water washing tower 2, the alkali washing tower 3, the dryer 4, and the deethanizer 6 are treated, and then enter the carbon two hydrogenation reactor 7 for selective hydrogenation to remove a trace amount of acetylene, and then enter
  • the demethanizer 5 is treated, wherein a compressor 8 is provided between the water wash column 2 and the alkali wash column 3, between the deethanizer column 6 and the carbon two hydrogenation reactor 7.
  • the reaction is carried out using a carbon two hydrogenation reactor equipped with a gas distribution system, which is a fixed bed Adiabatic reactor.
  • the reaction mass was from the top of the deethanizer column and its composition is shown in Table 3.
  • the above (Pd-Pb)/Al 2 O 3 catalyst was placed in a fixed bed reactor, and a mixed gas having a molar ratio of N 2 :H 2 of 1:1 was used at a space velocity of 200 h -1 at 115 ° C.
  • the catalyst was subjected to a reduction treatment for 3 hours to obtain a reduced palladium-based supported hydrogenation catalyst S-4.
  • the content of Pd in the catalyst S-4 was measured to be 0.05 wt.%, and the content of Pb was 0.48 wt.%.
  • SAN polystyrene acrylonitrile
  • DMF dimethylformamide
  • SAN/Al 2 O 3 precursor was added to 1000 mL of deionized water, 85.2 g of ethylenediamine was added, stirred until completely dissolved, and refluxed for 1 hour. After cooling to room temperature, the solid reaction product was washed with deionized water. Neutral, then dried at 80 ° C for 5 hours to give a functionalized SAN/Al 2 O 3 precursor.
  • the above (Pd-Pb)/Al 2 O 3 catalyst was placed in a fixed bed reactor, and a mixed gas having a molar ratio of N 2 :H 2 of 1:1 was used at a space velocity of 200 h -1 at 115 ° C.
  • This catalyst was subjected to a reduction treatment for 3 hours to obtain a reduced palladium-based supported hydrogenation catalyst D-4.
  • the content of Pd in the catalyst D-4 was measured to be 0.05 wt.%, and the content of Pb was 0.48 wt.%.
  • Example 4 The catalysts prepared in Example 4 and Comparative Example 4 were respectively used in the pre-depropane pre-hydrogenation process of carbon distillate.
  • the process flow chart is roughly as shown in FIG. 3, and the carbon distillate obtained by steam cracking of petroleum hydrocarbons was sequentially passed.
  • the carbon dihydrogenation reactor 7 is further subjected to selective hydrogenation to remove a trace amount of acetylene, and then the catalyst is removed.
  • the methane column 5 is treated, wherein a compressor 8 is provided between the water washing column 2 and the alkali washing column 3, between the depropanizer column 11 and the carbon two hydrogenation reactor 7.
  • the two carbon dihydrogenation reactors are used in series to carry out the reaction, that is, the outlet materials of one reactor enter the two-stage reactor; each reactor has an independent gas distribution system; both reactors are fixed bed adiabatic reactors.
  • the reaction mass was from the top of the depropanizer column and its composition is shown in Table 5.
  • a spherical carrier of ⁇ 4.2 mm weighed 500 g of a spherical carrier of ⁇ 4.2 mm, specific surface area of 45.0 m 2 /g, pore volume of 0.35 ml/g, and bulk density of 0.77 g/cm 3 , which contained ⁇ -Al 2 O 3 460 g and titanium oxide 40 g. .
  • the pore size of the carrier is bimodal pore size distribution, and the pore diameter is 20 to 35 nm and 200 to 450 nm, respectively.
  • the above (Pd-Cu)/Al 2 O 3 catalyst was placed in a fixed bed reactor, and the catalyst was subjected to reduction treatment at 120 ° C for 3 hours with a purity of 99.9% of hydrogen at a space velocity of 200 h -1 .
  • the Pd content of the catalyst S-5 was measured to be 0.02 wt.%, and the Cu content was 0.04 wt.%.
  • a spherical carrier of ⁇ 4.2 mm weighed 500 g of a spherical carrier of ⁇ 4.2 mm, specific surface area of 45.0 m 2 /g, pore volume of 0.35 mL/g, and bulk density of 0.77 g/cm 3 , which contained ⁇ -Al 2 O 3 460 g and titanium oxide 40 g. .
  • the pore size of the carrier is bimodal pore size distribution, and the pore diameter is 20 to 35 nm and 200 to 450 nm, respectively.
  • CPE chlorinated polyethylene
  • the (Pd-Cu)-CPE/Al 2 O 3 precursor was calcined at 450 ° C for 8 hours in an air atmosphere to obtain a (Pd-Cu)/Al 2 O 3 catalyst.
  • the above (Pd-Cu)/Al 2 O 3 catalyst was placed in a fixed bed reactor, and the catalyst was subjected to reduction treatment at 120 ° C for 3 hours with a purity of 99.9% of hydrogen at a space velocity of 200 h -1 .
  • the content of Pd in the catalyst D-5 was measured to be a Pd content of 0.02 wt.% and a Cu content of 0.04 wt.%.
  • Example 5 The catalysts prepared in Example 5 and Comparative Example 5 were respectively used in the pre-depropanation hydrogenation process before the carbon distillate, and the process flow chart thereof is roughly as shown in FIG.
  • the two carbon dihydrogenation reactors are used in series to carry out the reaction, that is, the outlet materials of one reactor enter the two-stage reactor; each reactor has an independent gas distribution system; both reactors are fixed bed adiabatic reactors.
  • the reaction mass was from the top of the depropanizer column and its composition is shown in Table 7.
  • a spherical ⁇ -Al 2 O 3 carrier of 500 g of ⁇ 4.0 mm, specific surface area of 20.0 m 2 /g, pore volume of 0.48 mL/g, and bulk density of 0.87 g/cm 3 was weighed.
  • the pore size of the carrier is bimodal, and the pore diameter is 20 to 50 nm and 300 to 500 nm, respectively.
  • the above (Pd-Ag)/Al 2 O 3 catalyst was placed in a fixed bed reactor, and the catalyst was subjected to reduction treatment at 120 ° C for 3 hours with a purity of 99.9% of hydrogen at a space velocity of 200 h -1 .
  • the content of Pd in the catalyst S-6 was measured to be 0.04 wt.%, and the content of Ag was 0.20 wt.%.
  • a spherical ⁇ -Al 2 O 3 carrier of 500 g of ⁇ 4.0 mm, specific surface area of 20.0 m 2 /g, pore volume of 0.48 mL/g, and bulk density of 0.87 g/cm 3 was weighed.
  • the pore size of the carrier is bimodal, and the pore diameter is 20 to 50 nm and 300 to 500 nm, respectively.
  • PVC polyvinyl chloride
  • THF tetrahydrofuran
  • the above (Pd-Ag)/Al 2 O 3 catalyst was placed in a fixed bed reactor, and the catalyst was subjected to reduction treatment at 120 ° C for 3 hours with a purity of 99.9% of hydrogen at a space velocity of 200 h -1 .
  • the content of Pd in the catalyst D-6 was measured to be 0.038 wt.%, and the content of Ag was 0.19 wt.%.
  • Example 6 The catalysts prepared in Example 6 and Comparative Example 6 were respectively used in an ethylene refining process using a sequential separation process.
  • the process flow chart is shown in FIG. 4, and the carbon distillate obtained by steam cracking of petroleum hydrocarbons was sequentially passed through an oil washing tower. 1. After washing the tower 2, the caustic scrubber 3, the dryer 4, the demethanizer 5, and the deethanizer 6, the carbon dioxide is further added.
  • the hydrogen reactor 7 is subjected to selective hydrogenation to remove a trace amount of acetylene, and then sequentially processed through an ethylene rectification column 9 and an ethylene refining reactor 10, wherein between the water washing tower 2 and the caustic scrubber 3, the demethanizer A compressor 8 is provided between the 5 and the deethanizer 6.
  • the reaction is carried out using a carbon two hydrogenation reactor equipped with a gas distribution system which is a fixed bed adiabatic reactor.
  • the content of C 2 H 2 in the reaction mass entering the carbon two hydrogenation reactor was 5 ⁇ L/L.
  • a cylindrical ⁇ -Al 2 O 3 carrier of 500 g of ⁇ 3.5 mm, height 3.5 mm, specific surface area of 47.0 m 2 /g, pore volume of 0.30 mL/g, and bulk density of 0.70 g/cm 3 was weighed.
  • the carrier was modified with an alkaline earth metal element Mg to have a Mg content of 0.35 wt.%.
  • the pore size of the carrier is bimodal, and the pore diameter is 20 to 30 nm and 100 to 450 nm, respectively.
  • the above (Pd-Au)/Al 2 O 3 catalyst was placed in a fixed bed reactor, and the catalyst was subjected to reduction treatment at 120 ° C for 3 hours with a purity of 99.9% of hydrogen at a space velocity of 200 h -1 .
  • the content of Pd in the catalyst S-7 was measured to be 0.05 wt.%, and the content of Au was 0.02 wt.%.
  • a cylindrical ⁇ -Al 2 O 3 carrier of 500 g of ⁇ 3.5 mm, height 3.5 mm, specific surface area of 47.0 m 2 /g, pore volume of 0.30 mL/g, and bulk density of 0.70 g/cm 3 was weighed.
  • the carrier was modified with an alkaline earth metal element Mg to have a Mg content of 0.35 wt.%.
  • the pore size of the carrier is bimodal, and the pore diameter is 20 to 30 nm and 100 to 450 nm, respectively.
  • Pd(NO 3 ) 2 0.61g was dissolved in 300 mL of deionized water, and an appropriate amount of nitric acid was added to adjust the pH to 2.5 to obtain a solution; the carrier was immersed in the solution, and after stirring for 5 minutes, the residue was decanted. The solid reaction product was dried at 110 ° C for 6 hours to obtain a Pd / Al 2 O 3 precursor.
  • the above (Pd-Au)/Al 2 O 3 catalyst was placed in a fixed bed reactor, and the catalyst was subjected to reduction treatment at 120 ° C for 3 hours with a purity of 99.9% of hydrogen at a space velocity of 200 h -1 .
  • the content of Pd in the catalyst D-7 was measured to be 0.05 wt.%, and the content of Au was 0.02 wt.%.
  • Example 7 The catalysts prepared in Example 7 and Comparative Example 7 were respectively used in the ethylene refining process using the pre-deethanization hydrogenation process.
  • the process flow chart is shown in Figure 5, and the carbon dioxide obtained by steam cracking petroleum hydrocarbons was used.
  • the fraction is sequentially treated by the oil washing tower 1, the water washing tower 2, the alkali washing tower 3, the dryer 4, and the deethanizer 6, and then enters the carbon two hydrogenation reactor 7 for selective hydrogenation to remove trace amounts of acetylene. And then sequentially processed through the demethanizer 5, the ethylene rectification column 9, and the ethylene refining reactor 10, wherein between the water washing column 2 and the alkali washing column 3, the deethanizer 6 and the carbon dihydrogenation reactor 7 A compressor 8 is provided between.
  • the reaction is carried out using a carbon two hydrogenation reactor equipped with a gas distribution system which is a fixed bed adiabatic reactor.
  • the content of C 2 H 2 in the reaction mass entering the carbon two hydrogenation reactor was 15 ⁇ L/L.
  • a cylindrical ⁇ -Al 2 O 3 carrier of 500 g of ⁇ 4.5 mm, height 4.5 mm, specific surface area of 50.0 m 2 /g, pore volume of 0.31 mL/g, and bulk density of 0.73 g/cm 3 was weighed.
  • the carrier was modified with an alkaline earth metal element Mg to have a Mg content of 0.15 wt.%.
  • the carrier has a pore size of 20 to 220 nm.
  • the above (Pd+Ni)/Al 2 O 3 catalyst was placed in a fixed bed reactor, and the catalyst was subjected to reduction treatment at 120 ° C for 3 hours with a purity of 99.9% of hydrogen at a space velocity of 200 h -1 .
  • the content of Pd in the catalyst S-8 was measured to be a Pd content of 0.084% and a Ni content of 0.28 wt.%.
  • a cylindrical ⁇ -Al 2 O 3 carrier of 500 g of ⁇ 4.5 mm, height 4.5 mm, specific surface area of 50.0 m 2 /g, pore volume of 0.31 mL/g, and bulk density of 0.73 g/cm 3 was weighed.
  • the carrier was modified with an alkaline earth metal element Mg to have a Mg content of 0.15 wt.%.
  • the carrier has a pore size of 20 to 220 nm.
  • SAN polystyrene acrylonitrile
  • DMF dimethylformamide
  • the above SAN/Al 2 O 3 precursor was added to 1000 mL of deionized water, and 57.6 g of ethylenediamine was added thereto. After stirring until completely dissolved, the reaction was refluxed for 4 hours. After cooling to room temperature, the solid reaction product was washed with deionized water. Neutral, then dried at 80 ° C for 5 hours to give a functionalized SAN/Al 2 O 3 precursor.
  • Example 8 and Comparative Example 8 were respectively used in a methanol to olefin (MTO) process using a sequential separation scheme, and the process flow chart is as shown in FIG. 6, and the product prepared by the methanol ethylene reactor 13 was prepared. After passing through the separator 15, the caustic scrubber 3, the dryer 4, the demethanizer 5, and the deethanizer 6 for treatment; the overhead product of the deethanizer 6 is introduced into the carbon dihydrogenation reactor 7 for selectivity.
  • MTO methanol to olefin
  • the reaction is carried out using a carbon two hydrogenation reactor equipped with a gas distribution system which is a fixed bed adiabatic reactor.
  • the content of C 2 H 2 in the reaction mass entering the carbon two hydrogenation reactor was 10 ⁇ L/L.
  • material gas space velocity is 6000h -1
  • reaction pressure is 2.0MPa
  • reactor catalyst loading is 300mL
  • H 2 /C 2 H 2 in the reactor 5:1 (molar ratio)
  • after 500 hours of reaction The results are shown in Table 11.
  • the Na content of the carrier after modification with the alkali metal element Na was 0.12 wt.%.
  • the pore size of the carrier is bimodal pore size distribution, and the pore diameter is 20 to 35 nm and 200 to 450 nm, respectively.
  • the above (Pd-Cu)/Al 2 O 3 catalyst was placed in a fixed bed reactor, and the catalyst was subjected to reduction treatment at 120 ° C for 3 hours with a purity of 99.9% of hydrogen at a space velocity of 200 h -1 .
  • the content of Pd in the catalyst S-9 was measured to be 0.04 wt.%, and the content of Cu was 0.12 wt.%.
  • the Na content of the carrier after modification with the alkali metal element Na was 0.12 wt.%.
  • the pore size of the carrier is bimodal pore size distribution, and the pore diameter is 20 to 35 nm and 200 to 450 nm, respectively.
  • SAN polystyrene acrylonitrile
  • DMF dimethylformamide
  • the above SAN/Al 2 O 3 precursor was added to 1000 mL of deionized water, and 57.6 g of ethylenediamine was added thereto. After stirring until completely dissolved, the reaction was refluxed for 4 hours. After cooling to room temperature, the solid reaction product was washed with deionized water. Neutral, then dried at 80 ° C for 3 hours to give a functionalized SAN/Al 2 O 3 precursor.
  • the above (Pd-Cu)/Al 2 O 3 catalyst was placed in a fixed bed reactor, and the catalyst was subjected to reduction treatment at 120 ° C for 3 hours with a purity of 99.9% of hydrogen at a space velocity of 200 h -1 .
  • the content of Pd in the catalyst D-9 was measured to be 0.04 wt.%, and the content of Cu was 0.12 wt.%.
  • Example 9 The catalysts prepared in Example 9 and Comparative Example 9 were respectively used in the ethylene refining process using the pre-depropane pre-hydrogenation process, and the process flow chart is shown in FIG. 7 , and the carbon distillate obtained by steam cracking petroleum hydrocarbons was used.
  • the carbon secondary hydrogenation reactor 7 After passing through the oil washing tower 1, the water washing tower 2, the alkali washing tower 3, the dryer 4, and the depropanizer column 11, the carbon secondary hydrogenation reactor 7 is further subjected to selective hydrogenation to remove a trace amount of acetylene, and then The process is sequentially carried out through the demethanizer 5, the deethanizer 6, the ethylene rectification column 9, and the ethylene refining reactor 10, wherein between the water washing tower 2 and the caustic scrubber 3, the depropanizer column 11 and the carbon dihydrogenation A compressor 8 is provided between the reactors 7.
  • the reaction is carried out using a carbon two hydrogenation reactor equipped with a gas distribution system which is a fixed bed adiabatic reactor.
  • the content of C 2 H 2 in the reaction mass entering the carbon two hydrogenation reactor was 12 ⁇ L/L.
  • a spherical ⁇ -Al 2 O 3 carrier of 500 g of ⁇ 4.0 mm, specific surface area of 20.0 m 2 /g, pore volume of 0.52 mL/g, and bulk density of 0.85 g/cm 3 was weighed.
  • the carrier has a pore size of 80 to 350 nm.
  • a spherical ⁇ -Al 2 O 3 carrier of 500 g of ⁇ 4.0 mm, specific surface area of 20.0 m 2 /g, pore volume of 0.52 mL/g, and bulk density of 0.85 g/cm 3 was weighed.
  • the carrier has a pore size of 80 to 350 nm.
  • PVC polyvinyl chloride
  • THF tetrahydrofuran
  • Example 10 The catalysts prepared in Example 10 and Comparative Example 10 were respectively used in a methanol to olefin (MTO) process using a pre-depropane pre-hydrogenation process.
  • MTO methanol to olefin
  • the process flow chart is shown in FIG. a dimethyl ether reactor (ie, DME reactor) 16, a methanol-to-propylene reactor (ie, MTP reactor) 17, a pre-cooling separator 18, a quench separator 19, a four-stage compressor 20, a four-stage separator 21,
  • DME reactor dimethyl ether reactor
  • MTP reactor methanol-to-propylene reactor
  • pre-cooling separator a quench separator 19
  • a four-stage compressor 20 a four-stage separator 21
  • the reaction is carried out using a carbon two hydrogenation reactor equipped with a gas distribution system which is a fixed bed adiabatic reactor.
  • the content of C 2 H 2 in the reaction mass entering the carbon two hydrogenation reactor was 5.3 ⁇ L/L.
  • the pore size of the carrier is bimodal pore size distribution, and the pore diameter is 100-180 nm and 350-750 nm, respectively.
  • the above (Pd-Ag)/Al 2 O 3 catalyst was placed in a fixed bed reactor, and the catalyst was subjected to reduction treatment at 100 ° C for 4 hours with a purity of 99.9% of hydrogen at a space velocity of 300 h -1 .
  • the content of Pd in the catalyst S-11 was measured to be 0.03 wt.%, and the content of Ag was 0.15 wt.%.
  • the pore size of the carrier is bimodal pore size distribution, and the pore diameter is 100-180 nm and 350-750 nm, respectively.
  • the above (Pd-Ag)/Al 2 O 3 catalyst was placed in a fixed bed reactor, and the catalyst was subjected to reduction treatment at 100 ° C for 4 hours with a purity of 99.9% of hydrogen at a space velocity of 300 h -1 .
  • the content of Pd in the catalyst D-11 was measured to be 0.03 wt.%, and the content of Ag was 0.15 wt.%.
  • Example 11 The catalysts prepared in Example 11 and Comparative Example 11 were respectively used in the pre-depropanation hydrogenation process before the carbon distillate, and the process flow chart thereof is roughly shown in FIG.
  • the three carbon dihydrogenation reactors are used in series to carry out the reaction, that is, the outlet materials of one reactor enter the two-stage reactor, and the outlet materials of the second-stage reactor enter the three-stage reactor; each reactor has an independent gas distribution system;
  • the three reactors are all fixed bed adiabatic reactors.
  • the reaction mass was from the top of the depropanizer column and its composition is shown in Table 14.
  • the pore size of the carrier is bimodal pore size distribution, and the pore diameter is 100-180 nm and 350-750 nm, respectively.
  • the pore size of the carrier is bimodal pore size distribution, and the pore diameter is 100-180 nm and 350-750 nm, respectively.
  • Example 12 The catalysts prepared in Example 12 and Comparative Example 12 were respectively used in the pre-de-ethane dehydrogenation process before the carbon distillate, and the process flow chart is shown in FIG. 2 .
  • the reaction is carried out using a carbon two hydrogenation reactor equipped with a gas distribution system which is a fixed bed adiabatic reactor.
  • the reaction mass was from the top of the deethanizer column and its composition is shown in Table 16.
  • the catalyst prepared by the conventional impregnation method the catalyst prepared by using the carrier containing the chlorine-containing organic substance, and the catalyst prepared by grafting the functional group with the organic polymer compound and supported on the carrier are prepared.
  • the catalyst prepared by the method of the invention exhibits more excellent activity, selectivity and anti-coking when used in various acetylene selective hydrogenation processes. Performance, and the amount of green oil produced during the hydrogenation process is also greatly reduced, while the amount of green oil is reduced, the active center of the catalyst is reduced by by-products, the activity and selectivity of the catalyst are well maintained, and the service life of the catalyst is maintained. extend.

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Abstract

一种钯系负载型加氢催化剂及其制备方法与应用。该催化剂是通过以下方法制备：采用含有带羟基的联吡啶衍生物的有机溶液浸渍含有 Al 2O 3的载体，可选择地经干燥后再采用含有主活性组分钯离子和助活性组分M n +离子（ M 选自 Ag、 Au、 Ni、 Pb和 Cu 中的一种）的混合溶液浸渍，再可选择地经干燥后，经焙烧，得到所述的催化剂。制备得到的催化剂具有优异的加氢活性、乙烯选择性及抗结焦性能，可用于碳二馏分的选择性加氢工艺中。

Description

一种钯系负载型加氢催化剂及其制备方法与应用 技术领域
本发明涉及加氢催化剂技术领域，具体为一种钯系负载型加氢催化剂及其制备方法与应用。
背景技术
乙烯是石油化学工业最重要的基础原料之一，作为合成各种聚合物的单体，其一般是由石油烃(如乙烷、丙烷、丁烷、石脑油和轻柴油等)蒸汽裂解制得。经这种方法得到的以乙烯为主的C2馏分中还含有0.5％～2.5％(摩尔分数)的乙炔。乙炔的存在会使乙烯的聚合过程复杂化，并且会恶化聚合物性能。当用高压法生产聚乙烯时，由于乙炔的积累，会有爆炸的危险；另外，在生产聚乙烯时，乙炔的存在还会降低聚合催化剂活性，增加催化剂的消耗；所以必须将乙烯中的乙炔降到一定值以下，才能将其作为合成聚合物的单体。因此，作为乙烯工业主要产物的C2馏分，需要经过加氢除炔精制后，才能作为聚合级的生产原料，用于生产聚乙烯等下游产品。
目前工业中通常采用选择性加氢法和溶剂提取法除去C2馏分中的乙炔。溶剂提取法既可得到精乙烯，又可回收产品乙块，但其工艺流程复杂，操作难度较大。目前，催化选择性加氢的方法是乙炔转化为乙烯最经济和最普遍接受的方法。
在乙烯的生产过程中，催化选择性加氢的工艺一般分为前加氢工艺和后加氢工艺。前加氢工艺和后加氢工艺之分主要是基于加氢反应器的位置的不同，加氢反应器位于脱甲烷塔之前的称为前加氢工艺，加氢反应器位于脱甲烷塔之后的称为后加氢工艺。后加氢工艺主要以美国ABB鲁玛斯集团(ABB Lummus Global)开发的加氢工艺为代表，采用顺序分离流程，即依次脱除甲烷、乙烷后再进行C2馏分的加氢除乙炔，后加氢工艺在国内早期引进的乙烯生产系统中较为普遍。前加氢工艺又分为前脱乙烷前加氢和前脱丙烷前加氢两种工艺，分别由德国林德公司(Linde Group)和美国斯通-韦伯斯特工程公司(Stone&Webster Engineering Corporation)开发，前脱丙烷前加氢工艺的加氢反应器设置在脱丙烷塔之后脱甲烷塔之前，而前脱乙烷前加氢工艺的加氢反应器设置在脱乙烷塔之后脱甲烷塔之前。
C2、C3馏分中所含的炔烃和二烯烃，通常通过选择性加氢进行脱除，选择性加氢催化剂是通过将贵金属(如钯)负载在多孔的无机材料载体上得到的(例如US4762956中介绍的)。US4404124通过分步浸渍法制备了具有活性组分壳层的选择性加氢催化剂，可应用于C2、C3馏分的选择性加氢，以消除乙烯中的乙块和丙烯中的丙炔、丙二烯。 US5587348以氧化铝为载体，通过银与钯的复合，并加入碱金属的氟化物制备了性能优良的乙炔加氢催化剂；该催化剂具有减少绿油生成量，提高乙烯选择性，减少含氧化合物生成量的特点。US5519566公开了一种湿法还原制备银与钯催化剂的方法，通过在浸渍液中加入有机或无机还原剂，制备得到了银与钯双组分选择性加氢催化剂。
以上传统的选择性加氢催化剂均采用浸渍法制备，并且其活性组分均为Pd、Ag双金属。这些方法存在以下缺点：(1)受载体孔结构的影响，活性组分的分散不能精确控制，随机性较强；(2)受浸渍液表面张力、溶剂化效应的影响，金属活性组分前驱体以聚集体形式沉积于载体表面，不能形成均匀分布；(3)C2馏分加氢对催化剂选择性要求较高，助活性组分Ag与主活性组分Pd的相互作用是提高催化剂选择性的关键因素，传统方法制备的催化剂，由于钯盐溶液与银盐溶液不同的表面张力，在载体上无法形成Pd、Ag同层分布，Ag的助剂作用表现得不明显，必须通过加大Ag的用量来促进其助剂作用的发挥，由此导致氢的传递受到阻碍，齐聚反应发生的可能性增大，以至绿油生成量增多，影响催化剂的寿命。以上三个问题的发生容易导致金属活性组分的分散性差，反应的选择性低，进而影响到催化剂的性能。
US4714692采用微乳液的方法进行单一组分贵金属催化剂的制备。采用这种方法制备多组分催化剂时，仍然避免不了溶剂化效应对催化剂活性组分分布的影响。
CN102206130A、CN102205243A均是通过在载体上吸附特定的高分子化合物，在载体表面形成高分子链包覆层，以带有特定官能基的化合物与载体上的高分子链进行反应，使之具有能够与活性组分络合的官能基，通过活性组分在载体表面官能基上发生络合反应，保证活性组分有序和高度分散。采用这两种方法制备催化剂时，载体吸附特定的高分子化合物，是通过载体氧化铝的羟基与高分子化合物进行化学吸附，载体吸附高分子化合物的量将受到氧化铝羟基数量的限制；经过官能化的高分子链与钯离子的络合作用不强，有时活性组分负载量达不到要求，浸渍液中还残留部分活性组分，造成催化剂成本提高；并且采用这两种方法制备C2馏分加氢催化剂还存在工艺流程复杂的缺点。
CN104971698A公开了一种含有R1R2R3N+X-的氧化铝成型物及其制备方法和应用，其中所述的R1R2R3N+X-选自伯胺盐、仲铵盐、叔铵盐、季铵盐中一种或者几种，X选自氯、溴或碘，取代基可以为直链或支链烷基，也可以为环烷基、芳基，也可以为带羟基和/或带杂环取代基的烃基。该氧化铝成型物的制备方法是将含有氧化铝的载体成型干燥后，置于高压反应釜中，用适量R1R2R3N+X-溶液在室温至250℃进行热处理，降温后在40℃～250℃干燥，脱除多余的溶剂，制备得到含有R1R2R3N+X-的大比表面积、大孔体积的氧化铝载体。该载体特别适用于Mo-Ni系负载型加氢催化剂的制备，用于汽油、柴 油加氢，有助于提高催化剂加氢脱硫活性。但是，对于贵金属Pd系催化剂而言，由于该方法所采用的有机物中含有氯、溴或碘，活化后容易在催化剂表面形成强酸中心Cl-、Br-、I-，造成不饱和烯烃、炔烃、二烯烃聚合，导致“绿油”大量生成，催化剂结焦大幅增加，影响催化剂使用寿命；同时该方法制备的载体为大比表面积、大孔体积的载体，不适合于制备壳层分布的Pd系催化剂。
发明内容
为解决上述技术问题，本发明的目的在于提供一种性能更为优异的钯系负载型加氢催化剂及其制备方法与应用。本发明提供的催化剂制备方法使钯原子和另一种金属原子能够在载体上高度均匀分散，能够克服浸渍液表面张力及溶剂化效应对活性组分的分散性的不利影响。
为达到上述目的，本发明首先提供了一种钯系负载型加氢催化剂的制备方法，其包括以下步骤：采用含有带羟基的联吡啶衍生物的有机溶液浸渍含有Al2O3的载体，可选择地经干燥后再采用含有主活性组分钯离子(即2价钯阳离子)和助活性组分Mn+离子的混合溶液浸渍，其中M选自Ag、Au、Ni、Pb和Cu中的一种，再可选择地经干燥后，经焙烧，得到所述的钯系负载型加氢催化剂。
在本发明的制备方法中，带羟基的联吡啶衍生物与含有Al2O3的载体形成强吸附后，再与主活性组分Pd和助活性组分M的金属阳离子形成有机络合物，最后得到活性组分高度分散的Pd-M负载型催化剂。
更具体地，本发明的钯系负载型加氢催化剂的制备方法包括以下步骤：
(1)采用含有带羟基的联吡啶衍生物的有机溶液浸渍含有Al2O3的载体，可选择地经干燥(即可以进行干燥或不进行干燥)后，形成羟基-联吡啶/Al2O3前躯体；
(2)然后，采用含有钯离子和Mn+离子的混合溶液浸渍所述羟基-联吡啶/Al2O3前躯体，可选择地经干燥(即可以进行干燥或不进行干燥)后，形成(Pd-M)-羟基-联吡啶/Al2O3前躯体；
(3)再焙烧所述(Pd-M)-羟基-联吡啶/Al2O3前躯体，得到所述的钯系负载型加氢催化剂。
在上述的制备方法中，优选地，采用含有带羟基的联吡啶衍生物的有机溶液浸渍含有Al2O3的载体(即上述步骤(1))是在20℃～60℃进行的，并且浸渍的时间为2～24小时。之后的干燥的温度可以为60℃～150℃，时间可以为2～10小时。
在上述的制备方法中，优选地，采用含有钯离子和Mn+离子的混合溶液浸渍羟基- 联吡啶/Al2O3前躯体(即上述步骤(2))是在20℃～100℃(优选为30℃～100℃)进行的，并且浸渍的时间为2～24小时。之后的干燥的温度可以为60℃～150℃，时间可以为2～10小时。
在上述的制备方法中，优选地，所述焙烧(即上述步骤(3))的温度是300℃～600℃，时间为2～12小时。更优选地，所述焙烧的温度是350℃～600℃。此外，所述焙烧优选是在含氧气氛中进行的。
在上述的制备方法中，优选地，所采用的含有Al2O3的载体包括氧化铝和/或含有氧化铝及其他氧化物的混合物等。其中，所述的其他氧化物可以包括氧化硅、氧化钛、氧化镁和氧化钙等中一种或几种的组合。此外，载体中的Al2O3的晶型可以为γ、δ、θ、α或以上这些晶型中的几种的混合晶型，优选为θ、α或其混合晶型。
在上述的制备方法中，优选地，所采用的含有Al2O3的载体可以是球形、齿球形、圆柱形、圆环形、条形、三叶草形或四叶草形等。
在上述的制备方法中，优选地，所述带羟基的联吡啶衍生物包括带羟基的2,2’-联吡啶衍生物和/或带羟基的3,3’-联吡啶衍生物，更优选为带羟基的2,2’-联吡啶衍生物。
在本发明的制备方法中，所述含有带羟基的联吡啶衍生物的有机溶液中的溶剂可以为本领域常用的有机溶剂，例如乙醇和/或乙醚等。该溶剂的作用是使所述带羟基的联吡啶衍生物能够完全溶解，有利于其吸附于载体上。对于该溶剂的用量并不做特殊限制，只要能够使所述带羟基的联吡啶衍生物完全溶解即可。
在上述的制备方法中，优选地，所述带羟基的联吡啶衍生物与所述含有钯离子和Mn+离子的混合溶液中的Pd和M的摩尔比为1～100:1；更优选地，该摩尔比为5～80:1；最优选地，该摩尔比为20～60:1。
在上述的制备方法中，优选地，所述含有钯离子和Mn+离子的混合溶液可以为一种或几种钯的可溶性盐以及一种或几种M的可溶性盐的混合溶液。例如，可以是Pd(NO3)2、M(NO3)n的混合溶液。该混合溶液中钯盐和M盐的用量是依据催化剂中所需的Pd、M的含量决定的；优选地，当M为Ag时，该混合溶液中Ag与Pd的摩尔比为0.4～10:1；当M为Au时，该混合溶液中Au与Pd的摩尔比为0.5～15:1；当M为Ni时，该混合溶液中Ni与Pd的摩尔比为0.4～20:1；当M为Pb时，该混合溶液中Pb与Pd的摩尔比为1～10:1；当M为Cu时，该混合溶液中Cu与Pd的摩尔比为1～10:1。
在上述的制备方法中，优选地，所述含有钯离子和Mn+离子的混合溶液的pH值为1.5～4.0，更优选为2.0～4.0。可以采用常用的pH值调节剂对该混合溶液的pH值进行调节。
在本发明一优选的具体实施方式中，该钯系负载型加氢催化剂的制备方法可以包括以下步骤：
步骤(1)羟基-联吡啶/Al2O3前躯体的制备：
采用含有带羟基的联吡啶衍生物的有机溶液浸渍含有Al2O3的载体，并在20℃～60℃反应2～24小时，然后可选择地将反应产物在60℃～150℃干燥2～10小时，得到羟基-联吡啶/Al2O3前躯体；其中，优选地，所述含有带羟基的联吡啶衍生物的有机溶液的体积为所述含有Al2O3的载体的体积的80％以上(包括80％)；
步骤(2)(Pd-M)-羟基-联吡啶/Al2O3前躯体的制备：
采用pH值为1.5～4.0的含有钯离子和Mn+离子的混合溶液浸渍步骤(1)制备得到的羟基-联吡啶/Al2O3前躯体，并在30℃～100℃反应2～24小时，然后可选择地将反应产物在60℃～150℃干燥2～10小时，得到(Pd-M)-羟基-联吡啶/Al2O3前躯体(其中的羟基-联吡啶与(Pd+M)的摩尔比为1～100:1，优选为5～80:1，更优选为20～60:1)；其中，优选地，所述混合溶液的体积为所述羟基-联吡啶/Al2O3前躯体的体积的60％～200％；
步骤(3)钯系负载型加氢催化剂的制备：
将步骤(2)制备得到的(Pd-M)-羟基-联吡啶/Al2O3前躯体在300～600℃焙烧2～12小时，得到所述的钯系负载型加氢催化剂。
在本发明一具体实施方式中，上述的钯系负载型加氢催化剂的制备方法还包括以下步骤：在使用该钯系负载型加氢催化剂之前，先采用含氢气的气体对其进行还原处理，得到还原态钯系负载型加氢催化剂。
在本发明的制备方法中，首先，含有Al2O3的载体中的Al-O键会对带羟基的联吡啶衍生物中的羟基产生强吸附，使的带羟基的联吡啶衍生物负载到载体上，得到负载有官能化的分子链的前驱体。然后，该前驱体中来自羟基联吡啶的剩余的羟基(即与Al-O键吸附之后剩余的羟基)和/或氮基，与钯离子和Mn+离子发生络合反应，使钯离子和Mn+离子结合到吸附于载体上的分子链上，该络合反应是络合基-金属离子的原位化学反应，金属离子是通过化学反应而非物理吸附结合到分子链上，因此Pd、M的原子在分子链上是呈均匀有序分布，分子链上结合的Pd原子与M原子的数量与分子链上的羟基与氮基的数量成正比。之后，在焙烧过程中，Pd原子和M原子会在原位进行氧化反应，形成Pd-M共晶复合金属氧化物，制备得到钯系双金属负载型加氢催化剂。
本发明提供的制备方法主要具有以下优点：首先，由于含有Al2O3的载体中的Al-O键对带羟基的联吡啶衍生物中的羟基产生强吸附，因此可以有效确保载体对羟基联吡啶的吸附量，避免溶液中羟基联吡啶的损失；此外，由于吸附在载体上的羟基联吡啶的羟 基及氮基与主活性组分Pd、助活性组分M的络合能力强，因此可以确保溶液中的钯离子和Mn+离子反应完全，避免溶液中活性组分Pd和M的损失，降低生产成本，并且使金属原子能够在载体上高度均匀分散；同时，该制备方法克服了浸渍液表面张力及溶剂化效应对Pd和M在载体上的分散的不利影响。采用本发明的制备方法制备得到的催化剂具有优异的加氢活性、乙烯选择性及抗结焦性能。
另一方面，本发明还提供了一种钯系负载型加氢催化剂，其是由上述的钯系负载型加氢催化剂的制备方法制备得到的。该催化剂具有优异的活性、选择性及抗结焦性能。
根据本发明的具体实施方式，优选地，以所述钯系负载型加氢催化剂的质量为100％计，该催化剂中Pd的含量为0.01％～0.8％；当M为Ag时，其含量为0.03％～3％，当M为Au时，其含量为0.02～0.25％，当M为Ni时，其含量为0.04～3％，当M为Pb时，其含量为0.04～3％，当M为Cu时，其含量为0.02～1％。
根据本发明的具体实施方式，优选地，所述钯系负载型加氢催化剂的比表面积为1～200m2/g，孔体积为0.15～0.8mL/g，堆密度为0.5～1.2g/cm3。
此外，本发明还提供了上述钯系负载型加氢催化剂在乙炔选择性加氢工艺中的应用。
在上述应用中，优选地，所述乙炔选择性加氢工艺为微量乙炔的选择性加氢工艺。
在上述应用中，优选地，所述乙炔选择性加氢工艺包括碳二馏分前脱丙烷前加氢工艺、碳二馏分前脱乙烷前加氢工艺、碳二馏分后加氢工艺、乙烯精制制备聚合级乙烯过程中的乙炔选择性加氢工艺、以及甲醇制烯烃过程中的乙炔选择性加氢工艺。
综上所述，本发明提供的催化剂制备方法使Pd原子和M原子在载体上高度均匀分散，克服了浸渍液表面张力及溶剂化效应对活性组分的分散性的不利影响。本发明提供的钯系负载型加氢催化剂具有优异的加氢活性、乙烯选择性及抗结焦性能，能够用于催化微量乙炔的选择性加氢。
附图说明
图1为采用顺序分离流程的碳二馏分后加氢工艺的流程图；
图2为碳二馏分前脱乙烷前加氢工艺的流程图；
图3为碳二馏分前脱丙烷前加氢工艺的流程图；
图4为采用顺序分离流程的乙烯精制工艺的流程图；
图5为采用前脱乙烷前加氢工艺流程的乙烯精制工艺的流程图；
图6为采用顺序分离流程的甲醇制烯烃(MTO)工艺的流程图；
图7为采用前脱丙烷前加氢工艺流程的乙烯精制工艺的流程图；
图8为采用前脱丙烷前加氢工艺流程的甲醇制烯烃(MTO)工艺的流程图；
主要组件符号说明：
1—油洗塔、2—水洗塔、3—碱洗塔、4—干燥器、5—脱甲烷塔、6—脱乙烷塔、7—碳二加氢反应器、8—压缩机、9—乙烯精馏塔、10—乙烯精制反应器、11—脱丙烷塔、12—丙烯精馏塔、13—甲醇制乙烯反应器、14—再生器、15—分离器、16—甲醇脱水制二甲醚反应器、17—甲醇制丙烯反应器、18—预急冷分离器、19—急冷分离器、20—四级压缩机、21—四级分离器。
具体实施方式
分析测试方法：
比表面积：按照标准GB/T-5816；
孔体积：按照标准GB/T-5816；
堆密度：按照标准Q/SY142-2006；
催化剂中Pd、Ag、Au、Ni、Cu或Pb含量：采用等离子体发射光谱仪或原子吸收光谱仪(按照标准GB/T 1537-94)；
乙烯选择性＝(反应后乙烯的摩尔百分含量-反应前乙烯的摩尔百分含量)/(反应前乙炔的摩尔百分含量-反应后乙炔的摩尔百分含量)。
实施例1
称取Φ3.5mm，比表面积为20.0m2/g，孔体积为0.48mL/g，堆密度为0.82g/cm3的球形α-Al2O3载体500g。载体孔径呈双峰孔径分布，孔径分别为20～50nm，300～500nm。
将34.12g 4,4’-二羟基-2,2’-联吡啶溶于650mL乙醇中，得到一溶液；将上述载体浸渍于该溶液中，静置2小时，使溶液中的4,4’-二羟基-2,2’-联吡啶完全负载到载体上后，将固体反应产物在60℃干燥10小时，得到羟基-联吡啶/Al2O3前躯体。
将0.37g Pd(NO3)2、0.79g AgNO3溶于600mL去离子水中，再加入适量硝酸调节pH值为3.5，得到一混合溶液；将上述羟基-联吡啶/Al2O3前躯体加入到该混合溶液中，搅拌10分钟后，静置2小时，倾出残液，将固体反应产物在120℃干燥4小时，得到(Pd-Ag)-羟基-联吡啶/Al2O3前躯体(其中的羟基-联吡啶与(Pd+Ag)的摩尔比为30)。
将上述(Pd-Ag)-羟基-联吡啶/Al2O3前躯体在550℃、空气气氛中焙烧3小时，得到(Pd-Ag)/Al2O3催化剂。
将上述(Pd-Ag)/Al2O3催化剂放置于固定床反应装置中，用纯度为99.9％的氢气，以 200h-1的空速，在120℃对该催化剂进行还原处理3小时，得到还原态钯系负载型加氢催化剂S-1。测得该催化剂S-1中Pd的含量为0.03wt.％，Ag的含量为0.10wt.％。
对比例1
称取Φ3.5mm，比表面积为20.0m2/g，孔体积为0.48mL/g，堆密度为0.82g/cm3的球形α-Al2O3载体500g。载体孔径呈双峰孔径分布，孔径分别为20～50nm，300～500nm。
将8.9g聚氯乙烯(PVC)溶于800mL四氢呋喃(THF)中，得到一溶液；将上述载体浸渍于该溶液中，静置2小时，使溶液中的PVC吸附于载体表面，将固体反应产物在60℃干燥10小时，得到PVC/Al2O3前躯体。
将19.28g双氰胺、4.0g Na2CO3加热溶于1000mL去离子水中，再加入上述PVC/Al2O3前躯体，回流反应1小时，冷却至室温后，将固体反应产物用去离子水洗涤至中性，然后在60℃干燥10小时，得到官能化的PVC/Al2O3前躯体。
将0.37g Pd(NO3)、0.79g AgNO3溶于600mL去离子水中，再加入适量硝酸调节pH值为3.5，得到一混合溶液；将上述官能化的PVC/Al2O3前躯体加入到该混合溶液中，搅拌0.5小时，倾出残液，将固体反应产物用去离子水洗涤至中性，然后在120℃干燥4小时，得到(Pd-Ag)-PVC/Al2O3前驱体。
将上述(Pd-Ag)-PVC/Al2O3前驱体在550℃、空气气氛中焙烧2小时，得到(Pd-Ag)/Al2O3催化剂。
将上述(Pd-Ag)/Al2O3催化剂放置于固定床反应装置中，用纯度为99.9％的氢气，以200h-1的空速，在120℃对该催化剂进行还原处理3小时，得到还原态钯系负载型加氢催化剂D-1。测得该催化剂D-1中Pd的含量为0.03wt.％，Ag的含量为0.10wt.％。
催化剂应用
将实施例1与对比例1制备得到的催化剂分别用于采用顺序分离流程的碳二馏分后加氢工艺中，其工艺流程图如图1所示，将石油烃蒸汽裂解得到的碳二馏分依次经过油洗塔1、水洗塔2、碱洗塔3、干燥器4、脱甲烷塔5、脱乙烷塔6进行处理之后，再进入碳二加氢反应器7进行选择性加氢以脱除微量的乙炔，其中，在水洗塔2和碱洗塔3之间、脱甲烷塔5和脱乙烷塔6之间设置压缩机8。
采用两个碳二加氢反应器串联进行反应，即一段反应器的出口物料进入二段反应器；每个反应器均有独立的配气系统；两个反应器均为固定床绝热反应器。
进入碳二加氢反应器进行处理的碳二物料的组成为：C2H21.58％、C2H4 81.55％和C2H616.87％(以体积百分含量计)。
反应条件：物料气体空速为2000h-1，反应压力为1.7MPa，两个反应器的催化剂装 填量均为450mL，一段反应器中的H2/C2H2＝1.5:1(摩尔比)，二段反应器中的H2/C2H2＝3:1(摩尔比)，反应500小时后的结果如表1所示。
表1
Figure PCTCN2016082976-appb-000001
实施例2
称取Φ2.5mm，比表面积为50m2/g，孔体积为0.75mL/g的球形载体500g，其含有θ-Al2O3 440g、氧化钛60g。
将6.82g 4,4’-二羟基-2,2’-联吡啶溶于600mL乙醇中，得到一溶液；将上述载体浸渍于该溶液中，静置8小时，使溶液中的4,4’-二羟基-2,2’-联吡啶完全负载到载体上后，将固体反应产物在110℃干燥6小时，得到羟基-联吡啶/Al2O3前躯体。
将0.38g氯化钯、1.72g氯金酸溶于600mL去离子水中，再加入适量盐酸调节pH值为2.5，得到一混合溶液；将上述羟基-联吡啶/Al2O3前躯体加入到该混合溶液中，搅拌1小时后，静置8小时，倾出残液，得到(Pd-Au)-羟基-联吡啶/Al2O3前躯体(其中的羟基-联吡啶与(Pd+Au)的摩尔比为5.03)。
将上述(Pd-Au)-羟基-联吡啶/Al2O3前躯体在500℃、空气气氛中焙烧6小时，得到(Pd-Au)/Al2O3催化剂S-2。测得该催化剂S-2中Pd的含量为0.045wt.％，Au的含量为0.20wt.％。
对比例2
称取Φ2.5mm，比表面积为50m2/g，孔体积为0.75mL/g的球形载体500g，其含有θ-Al2O3 440g、氧化钛60g。
将2.2g聚苯乙烯丙烯腈(SAN)加入到600mL二甲基甲酰胺(DMF)中，室温下搅拌至SAN完全溶解，得到一溶液；将上述载体加入到该溶液中，充分搅拌后静置1小时，将固体反应产物在120℃干燥6小时，得到SAN/Al2O3前驱体。
将上述SAN/Al2O3前躯体加入到1000mL去离子水中，再加入57.6g乙二胺，搅拌至完全溶解后回流反应1小时，冷却至室温后，将固体反应产物用去离子水洗涤至中性，然后在80℃干燥5小时，得到官能化的SAN/Al2O3前躯体。
将0.38g氯化钯、1.72g氯金酸溶于1200mL去离子水中，再加入适量盐酸调节pH 值为2.5，得到一混合溶液；取将上述官能化的SAN/Al2O3前驱体加入到该混合溶液中，搅拌2小时，倾出残液，将固体反应产物用去离子水洗涤至中性，得到(Pd-Au)-SAN/Al2O3前躯体。
将上述(Pd-Au)-SAN/Al2O3前躯体在380℃、空气气氛中焙烧2小时，得到(Pd-Au)/Al2O3催化剂D-2。测得该催化剂D-2中Pd的含量为0.045wt.％，Au的含量为0.20wt.％。
催化剂应用
将实施例2与对比例2制备得到的催化剂分别用于采用顺序分离流程的碳二馏分后加氢工艺，其工艺流程图如图1所示。
采用两个碳二加氢反应器串联进行反应，即一段反应器的出口物料进入二段反应器；每个反应器均有独立的配气系统；两个反应器均为固定床绝热反应器。
进入碳二加氢反应器进行处理的碳二物料的组成为：C2H21.7％、C2H474.3％和C2H624.0％(以体积百分含量计)。
反应条件：物料气体空速为4000h-1，反应压力为1.2MPa，两个反应器的催化剂装填量均为500mL，一段反应器中的H2/C2H2＝1.6:1(摩尔比)，二段反应器中的H2/C2H2＝2.8:1(摩尔比)，反应1000小时后的结果如表2所示。
表2
Figure PCTCN2016082976-appb-000002
实施例3
称取Φ4.5mm，高4.5mm，比表面积为17m2/g，孔体积为0.33mL/g的圆柱形载体500g，其含有α-Al2O3 400g、氧化镁100g。
将82.65g 6,6’-二羟基-3,3’-联吡啶溶于650mL乙醇中，得到一溶液；将上述载体浸渍于该溶液中，静置12小时，使溶液中的6,6’-二羟基-3,3’-联吡啶完全负载到载体上后，将固体反应产物在120℃干燥4小时，得到羟基-联吡啶/Al2O3前躯体。
将0.68g Pd(NO3)2、2.43g Ni(NO3)2·6H2O溶于600mL去离子水中，再加入适量硝酸调节pH值为3.4，得到一混合溶液；将上述羟基-联吡啶/Al2O3前躯体加入到该混合溶液中，搅拌60分钟后，静置10小时，倾出残液，得到(Pd-Ni)-羟基-联吡啶/Al2O3前躯 体(其中的羟基-联吡啶与(Pd+Ni)的摩尔比为40)。
将上述(Pd-Ni)-羟基-联吡啶/Al2O3前躯体在450℃、空气气氛中焙烧8小时，得到(Pd-Ni)/Al2O3催化剂。
将上述(Pd-Ni)/Al2O3催化剂放置于固定床反应装置中，用纯度为99.9％的氢气，以200h-1的空速，在120℃对该催化剂进行还原处理3小时，得到还原态钯系负载型加氢催化剂S-3。测得该催化剂S-3中Pd的含量为0.056wt.％，Ni的含量为0.098wt.％。
对比例3
称取Φ4.5mm，高4.5mm，比表面积为17m2/g，孔体积为0.33mL/g的圆柱形载体500g，其含有α-Al2O3 400g、氧化镁100g。
将8.9g聚氯乙烯(PVC)溶于800mL四氢呋喃(THF)中，得到一溶液；将上述载体浸渍于该溶液中，静置2小时，使溶液中的PVC吸附于载体表面，将固体反应产物在60℃干燥10小时，得到PVC/Al2O3前躯体。
将19.28g双氰胺、4.0g Na2CO3加热溶于1000mL去离子水中，再加入上述PVC/Al2O3前躯体，回流反应1小时，冷却至室温后，将固体反应产物用去离子水洗涤至中性，然后在60℃干燥10小时，得到官能化的PVC/Al2O3前躯体。
将0.68g Pd(NO3)2、2.43g Ni(NO3)2·6H2O溶于2400mL去离子水中，再加入适量硝酸调节pH值为3.4，得到一混合溶液；将上述官能化的PVC/Al2O3前躯体加入到该混合溶液中，搅拌0.5小时，倾出残液，将固体反应产物用去离子水洗涤至中性，然后在120℃干燥4小时，得到(Pd-Ni)-PVC/Al2O3前驱体。
将上述(Pd-Ni)-PVC/Al2O3前驱体在450℃、空气气氛中焙烧8小时，得到(Pd-Ni)/Al2O3催化剂。
将上述(Pd-Ni)/Al2O3催化剂放置于固定床反应装置中，用纯度为99.9％的氢气，以200h-1的空速，在120℃对该催化剂进行还原处理3小时，得到还原态钯系负载型加氢催化剂D-3。测得该催化剂D-3中Pd的含量为0.056wt.％，Ni的含量为0.098wt.％。
催化剂应用
将实施例3与对比例3制备得到的催化剂分别用于碳二馏分前脱乙烷前加氢工艺中，其工艺流程图如图2所示，将石油烃蒸汽裂解得到的碳二馏分依次经过油洗塔1、水洗塔2、碱洗塔3、干燥器4、脱乙烷塔6进行处理之后，再进入碳二加氢反应器7进行选择性加氢以脱除微量的乙炔，之后进入脱甲烷塔5进行处理，其中，在水洗塔2和碱洗塔3之间、脱乙烷塔6和碳二加氢反应器7之间设置压缩机8。
采用一个碳二加氢反应器进行反应，该反应器设置有配气系统，该反应器为固定床 绝热反应器。
反应物料来自脱乙烷塔塔顶，其组成如表3所示。
表3
加氢原料 H2 C2H2 C2H4 C2H6 CH4 CO
含量(v/v％) 25.32 0.5 34.3 8.88 31 0.005
反应条件：物料气体空速为7000h-1，反应压力为3.0MPa，反应器的催化剂装填量为500mL，反应500小时后的结果如表4所示。
表4
催化剂 入口温度(℃) 温升(℃) C2H2残余量(v/v％) 乙烯选择性(％) 绿油量(wt.％)
S-3 100 41 0.02 54 0.5
D-3 100 44 0.08 32 2.0
实施例4
称取Φ2.4mm，比表面积为18.0m2/g，孔体积为0.16mL/g的球形α-Al2O3载体500g。
将53.26g 4,4’-二羟基-2,2’-联吡啶溶于600mL乙醇中，得到一溶液；将上述载体浸渍于该溶液中，静置16小时，使溶液中的4,4’-二羟基-2,2’-联吡啶完全负载到载体上后，将固体反应产物在120℃干燥5小时，得到羟基-联吡啶/Al2O3前躯体。
将0.61g Pd(NO3)2、3.90g Pb(NO3)2溶于600mL去离子水中，再加入适量硝酸调节pH值为3.5，得到一混合溶液；将上述羟基-联吡啶/Al2O3前躯体加入到该混合溶液中，搅拌10分钟后，静置12小时，倾出残液，将固体反应产物在90℃干燥8小时，得到(Pd-Pb)-羟基-联吡啶/Al2O3前躯体(其中的羟基-联吡啶与(Pd+Pb)的摩尔比为20)。
将上述(Pd-Pb)-羟基-联吡啶/Al2O3前躯体在450℃、空气气氛中焙烧8小时，得到(Pd-Pb)/Al2O3催化剂。
将上述(Pd-Pb)/Al2O3催化剂放置于固定床反应装置中，用N2:H2的摩尔比为1:1的混合气体，以200h-1的空速，在115℃对该催化剂进行还原处理3小时，得到还原态钯系负载型加氢催化剂S-4。测得该催化剂S-4中Pd的含量为0.05wt.％，Pb的含量为0.48wt.％。
对比例4
称取Φ2.4mm，比表面积为18.0m2/g，孔体积为0.16mL/g的球形α-Al2O3载体500g。
将3.3g聚苯乙烯丙烯腈(SAN)加入到600mL二甲基甲酰胺(DMF)中，室温下搅拌至SAN完全溶解，得到一溶液；将上述载体加入到该溶液中，充分搅拌后静置1小时，将固体反应产物在120℃干燥6小时，得到SAN/Al2O3前驱体。
将上述SAN/Al2O3前躯体加入到1000mL去离子水中，再加入85.2g乙二胺，搅拌 至完全溶解后回流反应1小时，冷却至室温后，将固体反应产物用去离子水洗涤至中性，然后在80℃干燥5小时，得到官能化的SAN/Al2O3前躯体。
将0.61g Pd(NO3)2、3.90g Pb(NO3)2溶于1200mL去离子水中，再加入适量硝酸调节pH值为2.7，得到一混合溶液；将上述官能化的SAN/Al2O3前躯体加入到该混合溶液中，搅拌2小时，倾出残液，将固体反应产物用去离子水洗涤至中性，得到(Pd-Pb)-SAN/Al2O3前躯体。
将上述(Pd-Pb)-SAN/Al2O3前躯体在450℃、空气气氛中焙烧8小时，得到(Pd-Pb)/Al2O3催化剂。
将上述(Pd-Pb)/Al2O3催化剂放置于固定床反应装置中，用N2:H2的摩尔比为1:1的混合气体，以200h-1的空速，在115℃对该催化剂进行还原处理3小时，得到还原态钯系负载型加氢催化剂D-4。测得该催化剂D-4中Pd的含量为0.05wt.％，Pb的含量为0.48wt.％。
催化剂应用
将实施例4与对比例4制备得到的催化剂分别用于碳二馏分前脱丙烷前加氢工艺中，其工艺流程图大致如图3所示，将石油烃蒸汽裂解得到的碳二馏分依次经过油洗塔1、水洗塔2、碱洗塔3、干燥器4、脱丙烷塔11进行处理之后，再进入碳二加氢反应器7进行选择性加氢以脱除微量的乙炔，之后进入脱甲烷塔5进行处理，其中，在水洗塔2和碱洗塔3之间、脱丙烷塔11和碳二加氢反应器7之间设置压缩机8。
采用两个碳二加氢反应器串联进行反应，即一段反应器的出口物料进入二段反应器；每个反应器均有独立的配气系统；两个反应器均为固定床绝热反应器。
反应物料来自脱丙烷塔塔顶，其组成如表5所示。
表5
加氢原料 H2 C2H2 C2H4 C2H6 CH4 C3H6 C3H8 PDMA CO C4 +
含量(v/v％) 18 0.6 33 6.2 26.2 13 2 0.8 0.2 0.47
反应条件：物料气体空速为4000h-1，反应压力为3.5MPa，两个反应器的催化剂装填量均为500mL，反应200小时后的结果如表6所示。
表6
Figure PCTCN2016082976-appb-000003
Figure PCTCN2016082976-appb-000004
实施例5
称取Φ4.2mm，比表面积为45.0m2/g，孔体积为0.35ml/g，堆密度为0.77g/cm3的齿球形载体500g，其含有θ-Al2O3 460g、氧化钛40g。载体孔径呈双峰孔径分布，孔径分别为20～35nm，200～450nm。
将15.79g 6,6'-二羟基-3,3'-联吡啶溶于650mL乙醇中，得到一溶液；将上述载体浸渍于该溶液中，静置12小时，使溶液中的6,6'-二羟基-3,3'-联吡啶完全负载到载体上后，将固体反应产物在120℃干燥4小时，得到羟基-联吡啶/Al2O3前躯体。
将0.25g Pd(NO3)2、0.59g Cu(NO3)2溶于600mL去离子水中，再加入适量硝酸调节pH值为2.1，得到一混合溶液；将上述羟基-联吡啶/Al2O3前躯体加入到该混合溶液中，搅拌1小时后，静置8小时，倾出残液，将固体反应产物在100℃干燥8小时，得到(Pd-Cu)-羟基-联吡啶/Al2O3前躯体(其中的羟基-联吡啶与(Pd+Cu)的摩尔比为20)。
将上述(Pd-Cu)-羟基-联吡啶/Al2O3前躯体在450℃、空气气氛中焙烧6小时，得到(Pd+Cu)/Al2O3催化剂。
将上述(Pd-Cu)/Al2O3催化剂放置于固定床反应装置中，用纯度为99.9％的氢气，以200h-1的空速，在120℃对该催化剂进行还原处理3小时，得到还原态钯系负载型加氢催化剂S-5。测得该催化剂S-5中Pd含量为0.02wt.％，Cu含量为0.04wt.％。
对比例5
称取Φ4.2mm，比表面积为45.0m2/g，孔体积为0.35mL/g，堆密度为0.77g/cm3的齿球形载体500g，其含有θ-Al2O3 460g、氧化钛40g。载体孔径呈双峰孔径分布，孔径分别为20～35nm，200～450nm。
将16.0g氯化聚乙烯(CPE)溶于800mL四氢呋喃(THF)中，然后加入480g双氰胺和4.0g Na2CO3，搅拌至完全溶解后回流反应2小时，冷却至室温后，将反应产物用去离子水洗涤至中性，得到官能化CPE溶液。
将0.25g Pd(NO3)2、0.59g Cu(NO3)2以及1mL硝酸，加入到上述官能化CPE溶液中， 搅拌1小时，得到(Pd-Cu)-CPE前驱体溶液。
将上述载体加入到上述(Pd-Cu)-CPE前驱体溶液中，充分搅拌后，静置4小时，倾出残液，将固体反应产物用去离子水洗涤至中性，然后在100℃干燥8小时，得到(Pd-Cu)-CPE/Al2O3前驱体。
将上述(Pd-Cu)-CPE/Al2O3前驱体在450℃、空气气氛中焙烧8小时，得到(Pd-Cu)/Al2O3催化剂。
将上述(Pd-Cu)/Al2O3催化剂放置于固定床反应装置中，用纯度为99.9％的氢气，以200h-1的空速，在120℃对该催化剂进行还原处理3小时，得到还原态钯系负载型加氢催化剂D-5。测得该催化剂D-5中Pd的含量为Pd含量为0.02wt.％，Cu含量为0.04wt.％。
催化剂应用
将实施例5与对比例5制备得到的催化剂分别用于碳二馏分前脱丙烷前加氢工艺中，其工艺流程图大致如图3所示。
采用两个碳二加氢反应器串联进行反应，即一段反应器的出口物料进入二段反应器；每个反应器均有独立的配气系统；两个反应器均为固定床绝热反应器。
反应物料来自脱丙烷塔塔顶，其组成如表7所示。
表7
加氢原料 H2 C2H2 C2H4 C2H6 CH4 C3H6 C3H8 PDMA CO C4 +
含量(v/v％) 18.0 0.7 35.6 6.2 24.5 11 3.0 0.6 0.2 0.3
反应条件：物料气体空速为8000h-1，反应压力为3.6MPa，两个反应器的催化剂装填量均为500mL，反应1000小时后的结果如表8所示。
表8
Figure PCTCN2016082976-appb-000005
实施例6
称取Φ4.0mm，比表面积为20.0m2/g，孔体积为0.48mL/g，堆密度为0.87g/cm3的球形α-Al2O3载体500g。载体孔径呈双峰孔径分布，孔径分别为20～50nm，300～500nm。
将167.81g 4,4’-二羟基-2,2’-联吡啶溶于650mL乙醇中，得到一溶液；将上述载体浸渍于该溶液中，静置2小时，使溶液中的4,4’-二羟基-2,2’-联吡啶完全负载到Al2O3载体上后，将固体反应产物在60℃干燥10小时，得到羟基-联吡啶/Al2O3前躯体。
将0.49g Pd(NO3)2、1.57g AgNO3溶于600mL去离子水中，再加入适量硝酸调节pH值为2.7，得到一混合溶液；将上述羟基-联吡啶/Al2O3前躯体加入到该混合溶液中，搅拌10分钟后，静置2小时，倾出残液，将固体反应产物在120℃干燥4小时，得到(Pd-Ag)-羟基-联吡啶/Al2O3前躯体(其中的羟基-联吡啶与(Pd+Ag)的摩尔比为80)。
将上述(Pd-Ag)-羟基-联吡啶/Al2O3前躯体在550℃、空气气氛中焙烧2小时，得到(Pd-Ag)/Al2O3催化剂。
将上述(Pd-Ag)/Al2O3催化剂放置于固定床反应装置中，用纯度为99.9％的氢气，以200h-1的空速，在120℃对该催化剂进行还原处理3小时，得到还原态钯系负载型加氢催化剂S-6。测得该催化剂S-6中Pd的含量为0.04wt.％，Ag的含量为0.20wt.％。
对比例6
称取Φ4.0mm，比表面积为20.0m2/g，孔体积为0.48mL/g，堆密度为0.87g/cm3的球形α-Al2O3载体500g。载体孔径呈双峰孔径分布，孔径分别为20～50nm，300～500nm。
将8.9g聚氯乙烯(PVC)溶于800mL四氢呋喃(THF)中，得到一溶液；将上述载体浸渍于该溶液中，静置2小时，使溶液中的PVC吸附于载体表面，将固体反应产物在90℃干燥6小时，得到PVC/Al2O3前躯体。
将119.28g双氰胺、4.0g Na2CO3加热溶于1000mL去离子水中，再加入上述PVC/Al2O3前躯体，回流反应1小时，冷却至室温后，将固体反应产物用去离子水洗涤至中性，然后在60℃干燥10小时，得到官能化的PVC/Al2O3前躯体。
将0.49g Pd(NO3)、1.57g AgNO3溶于200mL去离子水中，再加入适量硝酸调节pH值为2.7，得到一混合溶液；将上述官能化的PVC/Al2O3前躯体加入到该混合溶液中，搅拌0.5小时，倾出残液，将固体反应产物用去离子水洗涤至中性，然后在120℃干燥4小时，得到(Pd-Ag)-PVC/Al2O3前驱体。
将上述(Pd-Ag)-PVC/Al2O3前驱体在550℃、空气气氛中焙烧2小时，得到(Pd-Ag)/Al2O3催化剂。
将上述(Pd-Ag)/Al2O3催化剂放置于固定床反应装置中，用纯度为99.9％的氢气，以200h-1的空速，在120℃对该催化剂进行还原处理3小时，得到还原态钯系负载型加氢催化剂D-6。测得该催化剂D-6中Pd的含量为0.038wt.％，Ag的含量为0.19wt.％。
催化剂应用
将实施例6与对比例6制备得到的催化剂分别用于采用顺序分离流程的乙烯精制工艺中，其工艺流程图如图4所示，将石油烃蒸汽裂解得到的碳二馏分依次经过油洗塔1、水洗塔2、碱洗塔3、干燥器4、脱甲烷塔5、脱乙烷塔6进行处理之后，再进入碳二加 氢反应器7进行选择性加氢以脱除微量的乙炔，然后依次经过乙烯精馏塔9、乙烯精制反应器10进行处理，其中，在水洗塔2和碱洗塔3之间、脱甲烷塔5和脱乙烷塔6之间设置压缩机8。
采用一个碳二加氢反应器进行反应，该反应器设置有配气系统，该反应器为固定床绝热反应器。
进入碳二加氢反应器的反应物料中C2H2的含量为5μL/L。
反应条件：物料气体空速为2500h-1，反应压力为2.0MPa，反应器催化剂装填量为200mL，反应器中的H2含量为10μL/L，反应500小时后的结果如表9所示。
表9
催化剂 反应器入口温度(℃) 温升(℃) C2H2残余量(μL/L) 乙烯选择性(％) 绿油量(g)
S-6 35 4 0 55 0.8
D-6 35 6 1.4 37 1.9
实施例7
称取Φ3.5mm，高3.5mm，比表面积为47.0m2/g，孔体积为0.30mL/g，堆密度为0.70g/cm3的圆柱形δ-Al2O3载体500g。该载体经碱土金属元素Mg进行改性后的Mg含量为0.35wt.％。载体孔径呈双峰孔径分布，孔径分别为20～30nm，100～450nm。
将5.30g 4,4’-二羟基-2,2’-联吡啶溶于600mL乙醇中，得到一溶液；将上述载体浸渍于该溶液中，静置10小时，使溶液中的4,4’-二羟基-2,2-联吡啶完全负载到载体上后，将固体反应产物在100℃干燥6小时，得到羟基-联吡啶/Al2O3前躯体。
将0.61g Pd(NO3)2、0.21g氯金酸溶于600mL去离子水中，再加入适量硝酸调节pH值为3.0，得到一混合溶液；将上述羟基-联吡啶/Al2O3前躯体加入到该混合溶液中，搅拌1小时后，静置10小时，倾出残液，将固体反应产物在90℃干燥10小时，得到(Pd-Au)-羟基-联吡啶/Al2O3前躯体(其中的羟基-联吡啶与(Pd+Au)的摩尔比为10)。
将上述(Pd-Au)-羟基-联吡啶/Al2O3前躯体在600℃、空气气氛中焙烧2小时，得到(Pd-Au)/Al2O3催化剂。
将上述(Pd-Au)/Al2O3催化剂放置于固定床反应装置中，用纯度为99.9％的氢气，以200h-1的空速，在120℃对该催化剂进行还原处理3小时，得到还原态钯系负载型加氢催化剂S-7。测得该催化剂S-7中Pd的含量为0.05wt.％，Au的含量为0.02wt.％。
对比例7
称取Φ3.5mm，高3.5mm，比表面积为47.0m2/g，孔体积为0.30mL/g，堆密度为0.70g/cm3的圆柱形δ-Al2O3载体500g。该载体经碱土金属元素Mg进行改性后的Mg含 量为0.35wt.％。载体孔径呈双峰孔径分布，孔径分别为20～30nm，100～450nm。
将0.61g Pd(NO3)2溶于300mL去离子水中，再加入适量硝酸调节pH值为2.5，得到一溶液；将上述载体浸渍于该溶液中，搅拌5分钟后，倾出残液，将固体反应产物在110℃干燥6小时，得到Pd/Al2O3前驱体。
将0.21g氯金酸溶于600mL去离子水中，得到一溶液；将上述Pd/Al2O3前驱体加入到该溶液中，搅拌5分钟后，倾出残液，将固体反应产物在110℃干燥6小时，然后在500℃、空气气氛中焙烧4小时，得到(Pd-Au)/Al2O3催化剂。
将上述(Pd-Au)/Al2O3催化剂放置于固定床反应装置中，用纯度为99.9％的氢气，以200h-1的空速，在120℃对该催化剂进行还原处理3小时，得到还原态钯系负载型加氢催化剂D-7。测得该催化剂D-7中Pd的含量为0.05wt.％，Au的含量为0.02wt.％。
催化剂应用
将实施例7与对比例7制备得到的催化剂分别用于采用前脱乙烷前加氢工艺流程的乙烯精制工艺中，其工艺流程图如图5所示，将石油烃蒸汽裂解得到的碳二馏分依次经过油洗塔1、水洗塔2、碱洗塔3、干燥器4、脱乙烷塔6进行处理之后，再进入碳二加氢反应器7进行选择性加氢以脱除微量的乙炔，然后依次经过脱甲烷塔5、乙烯精馏塔9、乙烯精制反应器10进行处理，其中，在水洗塔2和碱洗塔3之间、脱乙烷塔6和碳二加氢反应器7之间设置压缩机8。
采用一个碳二加氢反应器进行反应，该反应器设置有配气系统，该反应器为固定床绝热反应器。
进入碳二加氢反应器的反应物料中C2H2的含量为15μL/L。
反应条件：物料气体空速为8000h-1，反应压力为1.8MPa，反应器催化剂装填量为500mL，反应器中的H2/C2H2＝5:1(摩尔比)，反应100小时后的结果如表10所示。
表10
催化剂 反应器入口温度(℃) 温升(℃) C2H2残余量(μL/L) 乙烯选择性(％) 绿油量(g)
S-7 30 14 0 80 1.5
D-7 30 13 1.3 33 5.8
实施例8
称取Φ4.5mm，高4.5mm，比表面积为50.0m2/g，孔体积为0.31mL/g，堆密度为0.73g/cm3的圆柱形θ-Al2O3载体500g。该载体经碱土金属元素Mg进行改性后的Mg含量为0.15wt.％。载体孔径为20～220nm。
将130.79g g 4,4’-二羟基-2,2’-联吡啶溶于650mL乙醇中，得到一溶液；将上述载体 浸渍于该溶液中，静置8小时，使溶液中的4,4’二羟基-2,2’-联吡啶完全负载到载体上后，将固体反应产物在90℃干燥8小时，得到羟基-联吡啶/Al2O3前躯体。
将1.03gPd(NO3)2，6.94g Ni(NO3)2·6H2O溶于500mL去离子水中，再加入适量硝酸调节pH值为2.5，得到一混合溶液；将上述羟基-联吡啶/Al2O3前躯体加入到该混合溶液中，搅拌1小时后，静置8小时，倾出残液，将固体反应产物在110℃干燥6小时，得到(Pd-Ni)-羟基-联吡啶/Al2O3前躯体(其中的羟基-联吡啶与(Pd+Ni)的摩尔比为25)。
将上述(Pd-Ni)-羟基-联吡啶/Al2O3前躯体在500℃、空气气氛中焙烧4小时，得到(Pd-Ni)/Al2O3催化剂。
将上述(Pd+Ni)/Al2O3催化剂放置于固定床反应装置中，用纯度为99.9％的氢气，以200h-1的空速，在120℃对该催化剂进行还原处理3小时，得到还原态钯系负载型加氢催化剂S-8。测得该催化剂S-8中Pd的含量为Pd含量为0.084％，Ni含量为0.28wt.％。
对比例8
称取Φ4.5mm，高4.5mm，比表面积为50.0m2/g，孔体积为0.31mL/g，堆密度为0.73g/cm3的圆柱形θ-Al2O3载体500g。该载体经碱土金属元素Mg进行改性后的Mg含量为0.15wt.％。载体孔径为20～220nm。
将2.2g聚苯乙烯丙烯腈(SAN)加入到600mL二甲基甲酰胺(DMF)中，室温下搅拌至SAN完全溶解，得到一溶液；将上述载体加入到该溶液中，充分搅拌后静置1小时，将固体反应产物在80℃干燥5小时，得到SAN/Al2O3前躯体。
将上述SAN/Al2O3前躯体加入到1000mL去离子水中，再加入57.6g乙二胺，搅拌至完全溶解后回流反应4小时，冷却至室温后，将固体反应产物用去离子水洗涤至中性，然后在80℃干燥5小时，得到官能化的SAN/Al2O3前躯体。
将将1.03gPd(NO3)2，6.94g Ni(NO3)2·6H2O溶于500mL去离子水中，再加入适量硝酸调节pH值为2.5，得到一混合溶液；将上述官能化的SAN/Al2O3前躯体加入到该混合溶液中，搅拌5分钟，倾出残液，将固体反应产物用去离子水洗涤至中性，然后在100℃干燥3小时，得到(Pd-Ni)-SAN/Al2O3前驱体。
将上述(Pd-Ni)-SAN/Al2O3前驱体在450℃、空气气氛中焙烧4小时，得到(Pd-Ni)/Al2O3催化剂。
将上述(Pd-Ni)/Al2O3催化剂放置于固定床反应装置中，用纯度为99.9％的氢气，以200h-1的空速，在120℃对该催化剂进行还原处理3小时，得到还原态钯系负载型加氢催化剂D-8。测得该催化剂D-8中Pd的含量为0.084wt.％，Ni的含量为0.28wt.％。
催化剂应用
将实施例8与对比例8制备得到的催化剂分别用于采用顺序分离流程的甲醇制烯烃(MTO)工艺中，其工艺流程图如图6所示，将甲醇制乙烯反应器13制备得到的产品依次经过分离器15、碱洗塔3、干燥器4、脱甲烷塔5、脱乙烷塔6进行处理之后；使脱乙烷塔6的塔顶产物进入碳二加氢反应器7进行选择性加氢以脱除微量的乙炔，然后进入乙烯精制反应器10进行处理；使脱乙烷塔6的塔底产物依次进入丙烯精馏塔12、脱丙烷塔11进行处理；其中，甲醇制乙烯反应器13还与再生器14连接。
采用一个碳二加氢反应器进行反应，该反应器设置有配气系统，该反应器为固定床绝热反应器。
进入碳二加氢反应器的反应物料中C2H2的含量为10μL/L。
反应条件：物料气体空速为6000h-1，反应压力为2.0MPa，反应器催化剂装填量为300mL，反应器中的H2/C2H2＝5:1(摩尔比)，反应500小时后的结果如表11所示。
表11
催化剂 反应器入口温度(℃) 温升(℃) C2H2残余量(μL/L) 乙烯选择性(％) 绿油量(g)
S-8 32 6 0 45 1.8
D-8 32 9 0.2 12 2.9
实施例9
称取Φ4.5mm，高4.5mm，比表面积为48.0m2/g，孔体积为0.32mL/g，堆密度为0.73g/cm3的圆柱形Al2O3载体500g，Al2O3为δ和θ的混合晶型。该载体经碱金属元素Na进行改性后的Na含量为0.12wt.％。载体孔径呈双峰孔径分布，孔径分别为20～35nm，200～450nm。
将106.52g 4,4’-二羟基-2,2’-联吡啶溶于600mL乙醇中，得到一溶液；将上述载体浸渍于该溶液中，静置8小时，使溶液中的4,4’二羟基-2,2’-联吡啶完全负载到Al2O3载体上后，将固体反应产物在90℃干燥8小时，得到羟基-联吡啶/Al2O3前躯体。
将0.49g Pd(NO3)2、1.77g Cu(NO3)2溶于600mL去离子水中，再加入适量硝酸调节pH值为2.5，得到一混合溶液；将上述羟基-联吡啶/Al2O3前躯体加入到该混合溶液中，搅拌1小时后，静置8小时，倾出残液，将固体反应产物在110℃干燥8小时，得到(Pd-Cu)-羟基-联吡啶/Al2O3前躯体(其中的羟基-联吡啶与(Pd+Cu)的摩尔比为50)。
将上述(Pd-Cu)-羟基-联吡啶/Al2O3前躯体在500℃、空气气氛中焙烧4小时，得到(Pd-Cu)/Al2O3催化剂。
将上述(Pd-Cu)/Al2O3催化剂放置于固定床反应装置中，用纯度为99.9％的氢气，以200h-1的空速，在120℃对该催化剂进行还原处理3小时，得到还原态钯系负载型加氢 催化剂S-9。测得该催化剂S-9中Pd的含量为0.04wt.％，Cu的含量为0.12wt.％。
对比例9
称取Φ4.5mm，高4.5mm，比表面积为48.0m2/g，孔体积为0.32mL/g，堆密度为0.73g/cm3的圆柱形Al2O3载体500g，Al2O3为δ和θ的混合晶型。该载体经碱金属元素Na进行改性后的Na含量为0.12wt.％。载体孔径呈双峰孔径分布，孔径分别为20～35nm，200～450nm。
将2.2g聚苯乙烯丙烯腈(SAN)加入到600mL二甲基甲酰胺(DMF)中，室温下搅拌至SAN完全溶解，得到一溶液；将上述载体加入到该溶液中，充分搅拌后静置1小时，将固体反应产物在70℃干燥5小时，得到SAN/Al2O3前躯体。
将上述SAN/Al2O3前躯体加入到1000mL去离子水中，再加入57.6g乙二胺，搅拌至完全溶解后回流反应4小时，冷却至室温后，将固体反应产物用去离子水洗涤至中性，然后在80℃干燥3小时，得到官能化的SAN/Al2O3前躯体。
将0.49g Pd(NO3)2、1.77g Cu(NO3)2溶于600mL去离子水中，再加入适量硝酸调节pH值为2.5，得到一混合溶液；将上述官能化的SAN/Al2O3前躯体加入到该混合溶液中，搅拌5分钟，倾出残液，将固体反应产物用去离子水洗涤至中性，然后在120℃干燥5小时，得到(Pd-Cu)-SAN/Al2O3前驱体。
将上述(Pd-Cu)-SAN/Al2O3前驱体在500℃、空气气氛中焙烧4小时，得到(Pd-Cu)/Al2O3催化剂。
将上述(Pd-Cu)/Al2O3催化剂放置于固定床反应装置中，用纯度为99.9％的氢气，以200h-1的空速，在120℃对该催化剂进行还原处理3小时，得到还原态钯系负载型加氢催化剂D-9。测得该催化剂D-9中Pd的含量为0.04wt.％，Cu的含量为0.12wt.％。
催化剂应用
将实施例9与对比例9制备得到的催化剂分别用于采用前脱丙烷前加氢工艺流程的乙烯精制工艺中，其工艺流程图如图7所示，将石油烃蒸汽裂解得到的碳二馏分依次经过油洗塔1、水洗塔2、碱洗塔3、干燥器4、脱丙烷塔11进行处理之后，再进入碳二加氢反应器7进行选择性加氢以脱除微量的乙炔，然后依次经过脱甲烷塔5、脱乙烷塔6、乙烯精馏塔9、乙烯精制反应器10进行处理，其中，在水洗塔2和碱洗塔3之间、脱丙烷塔11和碳二加氢反应器7之间设置压缩机8。
采用一个碳二加氢反应器进行反应，该反应器设置有配气系统，该反应器为固定床绝热反应器。
进入碳二加氢反应器的反应物料中C2H2的含量为12μL/L。
反应条件：物料气体空速为20000h-1，反应压力为2.0MPa，反应器催化剂装填量为500mL，反应器中的H2/C2H2＝5.6:1(摩尔比)，反应1000小时后的结果如表12所示。
表12
催化剂 反应器入口温度(℃) 温升(℃) C2H2残余量(μL/L) 乙烯选择性(％) 绿油量(g)
S-9 32 11 0 69 0.8
D-9 32 12 0.5 17 2.7
实施例10
称取Φ4.0mm，比表面积为20.0m2/g，孔体积为0.52mL/g，堆密度为0.85g/cm3的球形α-Al2O3载体500g。载体孔径为80～350nm。
将69.5g 6,6'-二羟基-3,3'-联吡啶溶于700mL乙醇中，得到一溶液；将上述载体浸渍于该溶液中，静置2小时，使溶液中的6,6'-二羟基-3,3'-联吡啶完全负载到载体上后，将固体反应产物在60℃干燥10小时，得到羟基-联吡啶/Al2O3前躯体。
将0.49g Pd(NO3)2、1.82g Pb(NO3)2溶于600mL去离子水中，再加入适量硝酸调节pH值为2.7，得到一混合溶液；将上述羟基-联吡啶/Al2O3前躯体加入到该混合溶液中，搅拌10分钟后，静置2小时，倾出残液，将固体反应产物在120℃干燥4小时，得到(Pd-Pb)-羟基-联吡啶/Al2O3前躯体(其中的羟基-联吡啶与(Pd+Pb)的摩尔比为20)。
将上述(Pd-Pb)-羟基-联吡啶/Al2O3前躯体在550℃、空气气氛中焙烧2小时，得到(Pd-Pb)/Al2O3催化剂。
将上述(Pd-Pb)/Al2O3催化剂放置于固定床反应装置中，用纯度为99.9％的氢气，以200h-1的空速，在120℃对该催化剂进行还原处理3小时，得到还原态钯系负载型加氢催化剂S-10。测得该催化剂S-10中Pd的含量为0.04wt.％，Pb的含量为0.23wt.％。
对比例10
称取Φ4.0mm，比表面积为20.0m2/g，孔体积为0.52mL/g，堆密度为0.85g/cm3的球形α-Al2O3载体500g。载体孔径为80～350nm。
将8.9g聚氯乙烯(PVC)溶于800mL四氢呋喃(THF)中，得到一溶液；将上述载体浸渍于该溶液中，静置2小时，使溶液中的PVC吸附于载体表面，将固体反应产物在100℃干燥3小时，得到PVC/Al2O3前躯体。
将119.28g双氰胺、4.0g Na2CO3加热溶于1000mL去离子水中，再加入上述PVC/Al2O3前躯体，回流反应1小时，冷却至室温后，将固体反应产物用去离子水洗涤至中性，然后在60℃干燥10小时，得到官能化的PVC/Al2O3前躯体。
将0.49g Pd(NO3)2、1.82g Pb(NO3)2溶于600mL去离子水中，再加入适量硝酸调节 pH值为2.5，得到一混合溶液；将上述官能化的PVC/Al2O3前躯体加入到该混合溶液中，搅拌0.5小时，倾出残液，将固体反应产物用去离子水洗涤至中性，然后在120℃干燥4小时，得到(Pd-Pb)-PVC/Al2O3前驱体。
将上述(Pd-Pb)-PVC/Al2O3前驱体在550℃、空气气氛中焙烧2小时，得到(Pd-Pb)/Al2O3催化剂。
将上述(Pd-Pb)/Al2O3催化剂放置于固定床反应装置中，用纯度为99.9％的氢气，以200h-1的空速，在120℃对该催化剂进行还原处理3小时，得到还原态钯系负载型加氢催化剂D-10。测得该催化剂D-10中Pd的含量为0.04wt.％，Pb的含量为0.23wt.％。
催化剂应用
将实施例10与对比例10制备得到的催化剂分别用于采用前脱丙烷前加氢工艺流程的甲醇制烯烃(MTO)工艺中，其工艺流程图如图8所示，将甲醇依次经过甲醇脱水制二甲醚反应器(即DME反应器)16、甲醇制丙烯反应器(即MTP反应器)17、预急冷分离器18、急冷分离器19、四级压缩机20、四级分离器21、干燥器4进行处理之后，再进入碳二加氢反应器7进行选择性加氢以脱除微量的乙炔，然后依次经过脱甲烷塔5、脱乙烷塔6进行处理。
采用一个碳二加氢反应器进行反应，该反应器设置有配气系统，该反应器为固定床绝热反应器。
进入碳二加氢反应器的反应物料中C2H2的含量为5.3μL/L。
反应条件：物料气体空速为2700h-1，反应压力为2.0MPa，反应器催化剂装填量为500mL，反应器中的H2/C2H2＝5:1(摩尔比)，反应1000小时后的结果如表13所示。
表13
催化剂 反应器入口温度(℃) 温升(℃) C2H2残余量(μL/L) 乙烯选择性(％) 绿油量(g)
S-10 32 7 0 44 1.5
D-10 32 8 1.0 24 2.7
实施例11
称取Φ4.5mm，高4.5mm，比表面积为10.0m2/g，孔体积为0.21mL/g，堆密度为0.75g/cm3的圆柱形载体500g，其含有Al2O3 487.5g、氧化镁12.5g，其中Al2O3为θ、α的混合晶型。载体孔径呈双峰孔径分布，孔径分别为100～180nm，350～750nm。
将47.2g 6,6'-二羟基-3,3'-联吡啶溶于600mL乙醇中，得到一溶液；将上述载体浸渍于该溶液中，静置10小时，使溶液中的6,6'-二羟基-3,3'-联吡啶完全负载到载体上后，将固体反应产物在100℃干燥6小时，得到羟基-联吡啶/Al2O3前躯体。
将0.37g Pd(NO3)2、1.18g AgNO3溶于450mL去离子水中，再加入适量硝酸调节pH值为2.5，得到一混合溶液；将上述羟基-联吡啶/Al2O3前躯体加入到该混合溶液中，搅拌1小时后，静置10小时，倾出残液，将固体反应产物在90℃干燥10小时，得到(Pd-Ag)-羟基-联吡啶/Al2O3前躯体(其中的羟基-联吡啶与(Pd+Ag)的摩尔比为30)。
将上述(Pd-Ag)-羟基-联吡啶/Al2O3前躯体在600℃、空气气氛中焙烧2小时，得到(Pd-Ag)/Al2O3催化剂。
将上述(Pd-Ag)/Al2O3催化剂放置于固定床反应装置中，用纯度为99.9％的氢气，以300h-1的空速，在100℃对该催化剂进行还原处理4小时，得到还原态钯系负载型加氢催化剂S-11。测得该催化剂S-11中Pd的含量为0.03wt.％，Ag的含量为0.15wt.％。
对比例11
称取Φ4.5mm，高4.5mm，比表面积为10.0m2/g，孔体积为0.21mL/g，堆密度为0.75g/cm3的圆柱形载体500g，其含有Al2O3 487.5g、氧化镁12.5g，其中Al2O3为θ、α的混合晶型。载体孔径呈双峰孔径分布，孔径分别为100～180nm，350～750nm。
将0.37g Pd(NO3)2、1.18g AgNO3溶于450mL去离子水中，再加入适量硝酸调节pH值为2.5，得到一混合溶液；将该混合溶液喷淋至上述载体后震荡0.5小时，倾出残液，将固体反应产物在90℃干燥10小时后，在600℃、空气气氛中焙烧2小时，得到(Pd-Ag)/Al2O3催化剂。
将上述(Pd-Ag)/Al2O3催化剂放置于固定床反应装置中，用纯度为99.9％的氢气，以300h-1的空速，在100℃对该催化剂进行还原处理4小时，得到还原态钯系负载型加氢催化剂D-11。测得该催化剂D-11中Pd的含量为0.03wt.％，Ag的含量为0.15wt.％。
催化剂应用
将实施例11与对比例11制备得到的催化剂分别用于碳二馏分前脱丙烷前加氢工艺中，其工艺流程图大致如图3所示。
采用三个碳二加氢反应器串联进行反应，即一段反应器的出口物料进入二段反应器，二段反应器出口物料进入三段反应器；每个反应器均有独立的配气系统；三个反应器均为固定床绝热反应器。
反应物料来自脱丙烷塔塔顶，其组成如表14所示。
反应条件：物料气体空速为10000h-1，反应压力为3.9MPa，三个反应器的催化剂装填量均为500mL，反应1000小时后的结果如表15所示。
表14
  H2 C2H2 C2H4 C2H6 CH4 C3H6 C3H8 PDMA CO C4 +
含量(v/v％) 16.0 0.9 39.0 9.5 19.5 12 2.0 0.7 0.1 0.3
表15
Figure PCTCN2016082976-appb-000006
实施例12
称取Φ4.5mm，高4.5mm，比表面积为8.0m2/g，孔体积为0.38mL/g，堆密度为0.75g/cm3的圆柱形载体500g，其含有α-Al2O3 481.5g、氧化镁12.5g、氧化钙6g。载体孔径呈双峰孔径分布，孔径分别为100～180nm，350～750nm。
将16.68g 6,6'-二羟基-3,3'-联吡啶溶于650mL乙醇中，得到一溶液；将上述载体浸渍于该溶液中，静置12小时，使溶液中的6,6'-二羟基-3,3'-联吡啶完全负载到载体上后，将固体反应产物在120℃干燥4小时，得到羟基-联吡啶/Al2O3前躯体。
将0.49g Pd(NO3)2、0.83g Cu(NO3)2溶于600mL去离子水中，再加入适量硝酸调节pH值为2.5，得到一混合溶液；将上述羟基-联吡啶/Al2O3前躯体加入到该混合溶液中，搅拌1小时后，静置12小时，倾出残液，将固体反应产物在120℃干燥4小时，得到(Pd-Cu)-羟基-联吡啶/Al2O3前躯体(其中的羟基-联吡啶与(Pd+Cu)的摩尔比为15)。
将上述(Pd-Cu)-羟基-联吡啶/Al2O3前躯体在450℃、空气气氛中焙烧8小时，得到(Pd-Cu)/Al2O3催化剂S-12。测得该催化剂S-12中Pd的含量为0.04wt.％，Cu的含量为0.056wt.％。
对比例12
称取Φ4.5mm，高4.5mm，比表面积为8.0m2/g，孔体积为0.38mL/g，堆密度为0.75g/cm3的圆柱形载体500g，其含有α-Al2O3 481.5g、氧化镁12.5g、氧化钙6g。载体孔径呈双峰孔径分布，孔径分别为100～180nm，350～750nm。
将6.0g十二烷基吡啶盐酸盐溶于600mL乙醇中，得到一溶液；将上述载体浸渍于该溶液中，密闭于室温下静置48小时，然后将固体反应产物在120℃干燥4小时，得到含有C12H25C5H4N·HCl的Al2O3前躯体。
将0.49g Pd(NO3)2、0.83g Cu(NO3)2溶于600mL去离子水中，再加入适量硝酸调节pH值为2.5，得到一混合溶液；将上述含有C12H25C5H4N·HCl的Al2O3前躯体加入到该 混合溶液中，静置2小时，倾出残液，将固体反应产物在120℃干燥4小时，得到(Pd-Cu)-烷基吡啶盐酸盐/Al2O3前驱体。
将上述(Pd-Cu)-烷基吡啶盐酸盐/Al2O3前驱体在500℃、空气气氛中焙烧2小时，得到(Pd-Cu)/Al2O3催化剂D-12。测得该催化剂D-12中Pd的含量为0.04wt.％，Cu的含量为0.056wt.％。
催化剂应用
将实施例12与对比例12制备得到的催化剂分别用于碳二馏分前脱乙烷前加氢工艺中，其工艺流程图如图2所示。
采用一个碳二加氢反应器进行反应，该反应器设置有配气系统，该反应器为固定床绝热反应器。
反应物料来自脱乙烷塔塔顶，其组成如表16所示。
反应条件：物料气体空速为12000h-1，反应压力为3.6MPa，反应器催化剂装填量为500mL，反应1000小时后的结果如表17所示。
表16
  H2 C2H2 C2H4 C2H6 CH4 CO C4 +
含量(v/v％) 30 0.6 33.2 5.88 30 0.008 0.312
表17
Figure PCTCN2016082976-appb-000007
由上述实施例与对比例可以看出，与采用传统浸渍法制备得到的催化剂、采用含有含氯有机物的载体制备得到的催化剂以及采用有机高分子化合物接枝官能团并负载在载体上制备得到的催化剂相比，在活性组分含量相同时，采用本发明的方法制备得到的催化剂，在用于各种乙炔选择性加氢工艺中时，催化剂均表现出更为优异的活性、选择性及抗结焦性能，并且加氢过程中绿油的生成量也大幅度降低，同时绿油生成量的降低，减少了催化剂的活性中心被副产物覆盖，催化剂活性及选择性得以很好的保持，催化剂使用寿命延长。

Claims (15)

  1. 一种钯系负载型加氢催化剂的制备方法，其包括以下步骤：采用含有带羟基的联吡啶衍生物的有机溶液浸渍含有Al2O3的载体，可选择地经干燥后再采用含有主活性组分钯离子和助活性组分Mn+离子的混合溶液浸渍，其中M选自Ag、Au、Ni、Pb和Cu中的一种，再可选择地经干燥后，经焙烧，得到所述的钯系负载型加氢催化剂。
  2. 根据权利要求1所述的制备方法，其中，采用含有带羟基的联吡啶衍生物的有机溶液浸渍含有Al2O3的载体是在20℃～60℃进行的，并且浸渍的时间为2～24小时。
  3. 根据权利要求1所述的制备方法，其中，采用含有主活性组分钯离子和助活性组分Mn+离子的混合溶液浸渍羟基-联吡啶/Al2O3前躯体是在30℃～100℃进行的，并且浸渍的时间为2～24小时。
  4. 根据权利要求1所述的制备方法，其中，所述焙烧的温度是300℃～600℃，时间为2～12小时。
  5. 根据权利要求1所述的制备方法，其中，所述含有Al2O3的载体包括氧化铝和/或含有氧化铝及其它氧化物的混合物；其中，所述其他氧化物包括氧化硅、氧化钛、氧化镁和氧化钙中一种或几种的组合。
  6. 根据权利要求1所述的制备方法，其中，所述含有Al2O3的载体中的Al2O3的晶型为γ、δ、θ、α或以上这些晶型中的几种的混合晶型。
  7. 根据权利要求1所述的制备方法，其中，所述含有Al2O3的载体是球形、齿球形、圆柱形、圆环形、条形、三叶草形或四叶草形。
  8. 根据权利要求1所述的制备方法，其中，所述带羟基的联吡啶衍生物包括带羟基的2,2’-联吡啶衍生物和/或带羟基的3,3’-联吡啶衍生物。
  9. 根据权利要求1所述的制备方法，其中，所述带羟基的联吡啶衍生物与所述含有主活性组分钯离子和助活性组分Mn+离子的混合溶液中的钯和M的摩尔比为1～100:1。
  10. 根据权利要求1所述的制备方法，其中，在所述含有主活性组分钯离子和助活性组分Mn+离子的混合溶液中，当M为Ag时，Ag与Pd的摩尔比为0.4～10:1，当M为Au时，Au与Pd的摩尔比为0.5～15:1，当M为Ni时，Ni与Pd的摩尔比为0.4～20:1，当M为Pb时，Pb与Pd的摩尔比为1～10:1，当M为Cu时，Cu与Pd的摩尔比为1～10:1。
  11. 根据权利要求1所述的制备方法，其中，所述含有主活性组分钯离子和助活性组分Mn+离子的混合溶液的pH值为1.5～4.0。
  12. 根据权利要求1所述的制备方法，其还包括以下步骤：在使用所述钯系负载型 加氢催化剂之前，先采用含氢气的气体对其进行还原处理，得到还原态钯系负载型加氢催化剂。
  13. 一种钯系负载型加氢催化剂，其是由权利要求1-12任一项所述的钯系负载型加氢催化剂的制备方法制备得到的。
  14. 根据权利要求13所述的钯系负载型加氢催化剂，以所述钯系负载型加氢催化剂的质量为100％计，该催化剂中Pd的含量为0.01％～0.8％，当M为Ag时，其含量为0.03％～3％，当M为Au时，其含量为0.02～0.25％，当M为Ni时，其含量为0.04～3％，当M为Pb时，其含量为0.04～3％，当M为Cu时，其含量为0.02～1％；该催化剂的比表面积为1～200m2/g，孔体积为0.15～0.8mL/g，堆密度为0.5～1.2g/cm3。
  15. 权利要求13或14所述的钯系负载型加氢催化剂在乙炔选择性加氢工艺中的应用。
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