CN101913976A - Selective hydrogenation method for C2 fraction - Google Patents
Selective hydrogenation method for C2 fraction Download PDFInfo
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- CN101913976A CN101913976A CN2009100920987A CN200910092098A CN101913976A CN 101913976 A CN101913976 A CN 101913976A CN 2009100920987 A CN2009100920987 A CN 2009100920987A CN 200910092098 A CN200910092098 A CN 200910092098A CN 101913976 A CN101913976 A CN 101913976A
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Abstract
The invention provides a selective hydrogenation method for C2 fraction, which adopts a front-end hydrogenation process method of front-end deethanization and is characterized in that: a Pd-Ag catalyst is filled in a fixed bed reactor; the Pd-Ag catalyst takes Al2O3 as a carrier and contains 0.01-0.1% of Pd and 0.01-0.2% of Ag in terms of the mass of the catalyst; measured by a hydrogen and oxygen titration method, the total metal dispersion degree of Pd and Ag in the catalyst is 35-70%; the reaction conditions are that: the inlet temperature of the reactor is 55-100 DEG C, the reaction pressure is 2.5-4.5 MPa and the gaseous hourly space velocity is 5,000-25,000 h<-1>. Through the method of the invention, the reaction can be performed in an isothermal or adiabatic bed reactor, so the energy consumption is greatly reduced, the operation is convenient, temperature runaway is not easy to happen, the safety of the reaction system is improved and the economic benefits of the device are increased.
Description
Technical field
The present invention relates to a kind of selection method of hydrotreating, particularly a kind of C 2 fraction selective hydrogenation removes the method for acetylene.
Background technology
The production of ethene is the tap of petrochemical industry, the selection hydrogenation of the acetylene in the steam cracking product, the ethene processing industry there is important role, except the outlet acetylene content that guarantees hydrogenator is up to standard, selectivity of catalyst is good, can make the least possible generation ethane of ethene, significant to the yield of ethene, the raising device economic benefit that improve whole technological process.
In the present C-2-fraction acetylene hydrogenation, more and more Duo employing carbon two front-end hydrogenation technologies are the front-end hydrogenation processing method of front-end deethanization, reaction process is: the splitting gas that steam cracking produced is through washing, oil wash, after the alkali cleaning, at first pass through the front-end deethanization tower, its cat head material is carbon one, C-2-fraction and hydrogen, and what draw from the tower still is C3 fraction.The overhead product of cat head enters carbon two hydrogenators and selects hydrogenation, to remove acetylene wherein after overdraft.The characteristics of this technology be hydrogenator before demethanizing tower, therefore a large amount of hydrogen is arranged in reaction mass, it is particularly important that selectivity of catalyst shows, otherwise can be owing to more ethylene hydrogenation causes the catalyticreactor temperature runaway.Especially the front-end hydrogenation method of front-end deethanization, because the content of hydrogen is higher, the thermal capacitance of reaction mass is lower, the bed temperature rise is higher than the front-end hydrogenation method of predepropanization.In this case, the catalyzed reaction selectivity is low, and reactor just is easy to take place temperature runaway, and the operation of installing is brought threat.Therefore this technology has to adopt the isothermal bed bioreactor.
Fixedly during the isothermal bed bioreactor, reaction conditions is: 60～100 ℃ of reactor inlet temperatures, reaction pressure 3.5～4.5Mpa, gas volume air speed 6000～25000h
-1
Consist of C-2-fraction 45～55 (Φ %) in the material, acetylene 0.4～1.0% (Φ %), methane 20～30% (Φ %), hydrogen 18～25% (Φ %), CO 0.02～0.2 (Φ %).
When adopting the isothermal bed process, use shell and tube reactor, heat-eliminating medium is arranged, to take away the heat that reaction produces between tubulation.For this processing method, generally adopt ethane or ethene as heat-eliminating medium, its flow direction is opposite with the stream flow direction.Its flow must more accurately be controlled, so that the temperature-stable in the reactor is in suitable scope, temperature is crossed the low alkynes that easily takes place to leak, and the temperature height is easy temperature runaway again.At the device driving initial stage, the catalyst activity height, to temperature sensitive, especially true.
Patent US 4484015 discloses a kind of catalyzer, and adopting with Pd is main active ingredient, is carrier with the Alpha-alumina, adds promotor silver, with immersion process for preparing carbon two hydrogenation catalysts of excellent property.This catalyzer has the excessive hydrogenation that can effectively reduce ethene, reduces the risk of bed temperature runaway.
The disclosed Preparation of catalysts method of this patent is to adopt pickling process.Because the surface polarity group of alpha-alumina supports is few, the influence that is subjected to steeping fluid surface tension and solvation effect in the dipping of catalyzer and drying treatment process is especially obvious, and the metal active constituent presoma is deposited on carrier surface with aggregate form.In addition, can not form strong interaction between dipping back metal-salt species and the carrier, high-temperature roasting causes metallics migration gathering easily and forms big crystal grain.In reaction process, the catalyst activity component also can constantly be assembled, and causes activity to reduce gradually.
Summary of the invention
The object of the present invention is to provide a kind of method of C-2-fraction front-end hydrogenation, a kind of C-2-fraction front-end deethanization front-end hydrogenation processing method particularly is provided,, improved hydrogenation selectivity by selecting Pd, the Ag catalyzer of high degree of dispersion.
The inventor finds that the hydrogenation reaction that too much body phase hydrogen participates in can take place big crystal grain in the catalyzer, therefore; adopt the high catalyzer of active ingredient dispersity; reduced the quantity of body phase hydrogen, to the selectivity of raising hydrogenation reaction, and then the security of raising device operation has crucial meaning.
A kind of selection method of hydrotreating of C-2-fraction, adopt the front-end hydrogenation processing method of front-end deethanization, select hydrogenation with entering fixed-bed reactor from the overhead product of front-end deethanization tower in the ethylene unit, to remove alkynes wherein, it is characterized in that being equipped with in the fixed-bed reactor Pd-Ag series catalysts, the Pd-Ag series catalysts is meant with Al
2O
3Being carrier, is 100% in the quality of catalyzer, wherein contains Pd amount 0.01～0.1%; Containing the Ag amount is 0.01～0.2%, and total metal dispersity of Pd and Ag is 35～70% in the employing hydroxide titration method mensuration catalyzer, best 40～70%; Reaction conditions is: 55～100 ℃ of reactor inlet temperatures, reaction pressure 2.5～4.5MPa, gas volume air speed 5000～25000h
-1
After adopting this high score catalyzer several times, the selectivity of described reaction and specific activity traditional catalyst all are greatly improved.
The inventor finds, when selecting hydrogenation owing to employing method of the present invention, because the raising of reaction preference can be adopted fixedly adiabatic reactor reactor.Therefore fixed bed of the present invention both can be the isothermal bed bioreactor, also can be the adiabatic reactor reactor, can be single also can be more than two many bed bioreactors.
When reactor was the adiabatic reactor reactor, reactor inlet temperature was preferably 55～90 ℃, and reaction pressure is preferably 2.5～3.5MPa, and single bed bioreactor gas volume air speed is preferably 5000h
-1～20000h
-1
Reactor is during for fixing isothermal bed bioreactor, and reactor inlet temperature is preferably 60～100 ℃, and reaction pressure is preferably 3.5～4.5MPa, and single gas volume air speed is preferably 6000～25000h
-1
In the present invention, described Pd-Ag series catalysts is meant with Al
2O
3Being carrier, is 100% in the quality of catalyzer, wherein preferably contains Pd 0.015～0.05%; Contain Ag 0.02～0.2%.The specific surface area of catalyzer is 2～20m preferably
2/ g; Pore volume is 0.2～0.5ml/g preferably; Bulk density is 0.8～1.2g/cm preferably
3
The principle of this invention is: in selective hydrogenation reaction, raising along with employed catalyst activity component Pd, Ag dispersity, the quantity of the hydrogen that catalyst body is mutually adsorbed reduces significantly, and the probability of acetylene generation deep hydrogenation reduces greatly, and the catalyzed reaction selectivity is significantly improved.
Be not particularly limited the approach that employed catalyzer improves the active ingredient dispersity among the present invention, but preferably or the most preferred scheme of the present invention be to adopt synthetic layered composite metal hydroxides to prepare this catalyzer, not only the activity of such catalysts component has high degree of dispersion, and other performance of catalyzer is also very excellent, is particularly suitable for being used for method of the present invention.
Palladium-palladium-silver system supported catalyst is high metal dispersity so, and preferably catalyzer is to use and introduces with the form of layered composite metal hydroxides that the method for Pd, Ag obtains, and promptly when the preparation catalyzer, mainly contains Al
2O
3The hole in the synthetic preparation process that contains this catalyst precursor materials of LDHs of Pd, Ag and Al of original position, and adopt conventional pickling process or coprecipitation method can not obtain fully, the dispersity of traditional catalyst is 5～15%, typically as G-83C etc.At Al
2O
3The hole in the synthetic this method of LDHs that contains Pd, Ag and Al of original position can be divided into for two steps and carry out, at first prepare PdMgAl-CO
3-LDHs/Al
2O
3Presoma, refabrication PdMgAl-Ag-LDHs/Al
2O
3Presoma.The calcination for activation process also needs certainly, but condition adopts general conditions to get final product, as at 200～600 ℃ of roasting temperature 2～24h.Certainly the present invention does not get rid of other method acquisition of use yet.
Layered composite metal hydroxides (Layered Double Hydroxides, be called for short LDHs) be the novel inorganic functional material of a class, the vertical ordered arrangement of its two-dimentional laminate forms three-dimensional crystalline structure, atom on the laminate is with covalent bonds, between interlayer anion and the laminate with ionic linkage and a little less than other chemical bond combine.Tricationic on the LDHs laminate makes the laminate skeleton positively charged, and the negatively charged ion of interlayer opposite charges balances each other with it, makes whole crystal show electric neutrality.The outstanding feature of this class material is the interchangeability of Modulatory character, dispersing uniformity and the interlayer anion of laminate element, introduce the LDHs laminate if will have the divalent-metal ion and the trivalent metal ion of hydrogenation activity, to improve favourable species or object introducing interlayer to catalyst performance, be subjected to the influencing jointly of orientation effect of atom in the minimum and crystal of lattice energy, these metal active constituents and help catalyst component to disperse at LDHs presoma camber can be prepared the hydrogenation catalyst of excellent property.
Preparation of catalysts method of the present invention can prepare PdMgAl-CO earlier
3-LDHs/Al
2O
3Presoma prepares PdMgAl-Ag (complex)-LDHs/Al then
2O
3Presoma is again with PdMgAl-Ag (the complex)-LDHs/Al for preparing
2O
3The presoma roasting makes PdMgAl-Ag (complex)-LDHs change corresponding complex metal oxides into.
Method can comprise the steps: more specifically
A.PdMgAl-CO
3-LDHs/Al
2O
3The preparation of presoma
Palladium salt, magnesium salts and solubility organic amine be dissolved in be mixed with mixing solutions in the deionized water, its volume is Al
2O
380～120% of the total pore volume of carrier is with Al
2O
3Carrier drops in the mixing solutions solution is absorbed, and reacts 5～24h under 80～200 ℃ of temperature, and solid particulate is taken out in the cooling back, uses deionized water wash, and is dry under 80～120 ℃, obtains PdMgAl-CO
3-LDHs/Al
2O
3Presoma;
B.PdMgAl-Ag (complex)-LDHs/Al
2O
3The preparation of presoma
The title complex solion of preparation Ag, its volume is PdMgAl-CO
3-LDHs/Al
2O
390～110% of the pore volume of presoma, and to regulate the pH value be 3～6, the mole number of Ag and PdMgAl-CO
3-LDHs/Al
2O
3The ratio of the mole number of the Pd in the presoma is preferably 0.4～5;
With PdMgAl-CO
3-LDHs/Al
2O
3Presoma drops in the title complex solion of above-mentioned Ag, reacts 5～24h under 80～150 ℃ of temperature, and solid particulate is taken out in the cooling back, uses the deionized water thorough washing, and is dry under 80～120 ℃, obtains PdMgAl-Ag (complex)-LDHs/Al
2O
3Presoma;
C. Preparation of catalysts
PdMgAl-Ag (complex)-LDHs/Al with step B preparation
2O
3Presoma makes PdMgAl-Ag (complex)-LDHs change corresponding complex metal oxides at 250～600 ℃ of roasting temperature 2～24h; Be catalyzer.
Catalyzer can be positioned in the reaction unit before use, use H
2Or contain H
2Mixed gas, 80～250 ℃ of temperature, obtain going back the ortho states catalyzer.
Used palladium salt is can be preparation palladium series catalyst palladium salt commonly used, as Pd (NO
3)
22H
2O, PdCl
2Deng, magnesium salts is solubility magnesium salts commonly used in the catalyzer equally, as Mg (NO
3)
26H
2O, MgCl
26H
2O or MgSO
47H
2O etc.; The solubility organic amine, as being urea, hexamethylenetetramine etc., the title complex ion of Ag can be Ag (SCN)
2 -, Ag (EDTA)
3-Or Ag (S
2SO
3)
2-Deng.
Adopt temperature programmed reduction(TPR), dehydrogenation and hydroxide titration (TPR, H
2-TPD and HOT) these universal methods measure Pd in catalyst samples and the total metal dispersity of Ag (being positioned at the ratio of lip-deep Pd of Pd-Ag alloy microcrystalline and Ag atomicity and Pd and Ag atomicity sum) and all can reach 35～45% usually, in addition higher.Adopt the Pd-Ag/Al of traditional immersion process for preparing
2O
3Sample records its dispersity below 15% with aforesaid method.
The inventor also finds, when the catalyzer that adopts the active ingredient high dispersive carries out hydrogenation reaction, under isothermal bed process condition, catalyzer can move moving than traditional catalyst under the much lower condition of desired minimum safe air speed, improve the security of technological operation greatly, improved the essential safety degree of device operation.After adopting this catalyzer, the safe air speed of device can be reduced to 5000h
-1
The contriver also finds, after adopting method of hydrotreating of the present invention, under isothermal bed process condition, the passable range of reaction temperature of catalyzer move than traditional catalyst desired wide, reaction is difficult for temperature runaway takes place, and improves the security of technological operation greatly, reduces operation control difficulty.
The inventor finds, adopt method of hydrotreating of the present invention after, can change into adiabatic reactor such as traditional hotbed that waits, reduce the consumption of energy, simplified the operation of reactor greatly, improve reliability, significant to the steady running that improves device.
Description of drawings
Fig. 1 is the carbon two front-end hydrogenation technical process of front-end deethanization technology.
Among the figure: the 1-oil scrubber; The 2-water wash column; 3-alkali is inhaled tower; The 4-drying tower; 5-front-end deethanization tower; 6-carbon two hydrogenators; The 7-demethanizing tower.
Embodiment
Analytical procedure and standard:
Specific surface area: GB/T-5816
Pore volume: GB/T-5816
Catalyst P d, Ag assay: use plasma emission spectrometer to record.The total metal dispersity of Pd and Ag: hydroxide titration (HOT) method is measured the ratio be positioned at the lip-deep Pd of Pd-Ag alloy microcrystalline and Ag atomicity and Pd and Ag atomicity sum.
The selectivity method of calculation:
Ethylene selectivity: S=1-| Δ ethane/Δ acetylene |
Embodiment 1
Catalyzer adopts method preparation of the present invention.
Take by weighing spherical Al
2O
3Carrier 500g, its specific surface area is 8.3m
2/ g, pore volume are 0.20ml/g, and bulk density is 1.1g/cm
3
Take by weighing 0.44g Pd (NO again
3)
22H
2O, 5.33g Mg (NO
3)
26H
2O and 8.5g hexamethylenetetramine are dissolved in and are mixed with mixing solutions in the deionized water, and the volume of solution is 80ml.With spherical Al
2O
3In the carrier input mixing solutions solution is absorbed, then it is moved in container, react 5h under 200 ℃ of temperature, solid particulate is taken out in the cooling back, uses the deionized water thorough washing, and is dry under 120 ℃, obtains PdMgAl-CO
3-LDHs/Al
2O
3Presoma.
Take by weighing 1.57g AgNO
3With 1.3g NaSCN preparation Ag (CNS)
2 -The title complex solion, its volume 110ml, the pH value is 6.With PdMgAl-CO
3-LDHs/Al
2O
3Presoma drops in the title complex solion of above-mentioned Ag, and in react 5h under 150 ℃ of temperature, solid particulate is taken out in the cooling back, uses the deionized water thorough washing, and is dry under 110 ℃, obtains PdMgAl-Ag (CNS)
2-LDHs/Al
2O
3Presoma.
With PdMgAl-Ag (CNS)
2-LDHs/Al
2O
3Presoma is at 500 ℃ of roasting temperature 8h, makes PdMgAl-Ag (CNS)
2-LDHs/Al
2O
3Change corresponding complex metal oxides into; Be positioned over before the use in the fixed-bed reactor, use H
2100 ℃ of temperature, 4h is handled in reduction, obtains high-dispersion loading type palladium-silver catalyst.Recording this catalyst P d content is 0.035%, and Ag content is 0.2%, and Mg content is 0.1%, and the total metal dispersity of Pd and Ag is 35%.
Reaction raw materials: from the front-end deethanization column overhead, comprise methane, hydrogen, the two accounts for 40～55% of cumulative volume, ethane, ethene, acetylene account for 40～55% of cumulative volume, in addition, also have a spot of CO.Reaction raw materials is concrete to be formed as table 1:
Table 1 reaction raw materials is formed
| Hydrogenating materials | H 2 | C 2H 2 | C 2H 4 | C 2H 6 | CH 4 | CO |
| Content % (V/V) | 28 | 1.0 | 48 | 6.8 | 16 | 0.2 |
Reaction conditions: three sections isothermal bed bioreactors; Single hop reactor content volume space velocity: 15000h
-1, working pressure: 4.5MPa, each section reactor catalyst loadings: 800ml.
Comparative Examples 1
Used carrier is identical with embodiment 1.
Preparation of Catalyst: the method according to the embodiment 1 of patent US 4484015 prepares catalyzer, takes by weighing 0.29g PdCl
2, be dissolved in the 130ml deionized water, regulating the H value with dilute hydrochloric acid is 3.8, and the 500g carrier impregnation in the solution of being prepared, 100 ℃ of dryings 4 hours, is obtained catalyst A.90% of the Pd of catalyst A institute load is positioned at apart from catalyst surface 300 micrometer ranges.
Take by weighing 1.57g AgNO
3, 5.33g Mg (NO
3)
26H
2O is dissolved in the 150ml deionized water, and regulating pH value with rare nitric acid is 3.0, changes the dipping still over to, at room temperature floods 30min, and inclining unnecessary liquid, 120 ℃ of dryings 2 hours, is called catalyst B.
At 500 ℃ of roasting temperature 8h, make metal-salt change corresponding complex metal oxides into catalyst B; Be positioned over before the use in the fixed-bed reactor, 100 ℃ of temperature, 4h is handled in reduction, obtains high-dispersion loading type palladium-silver catalyst with H2.Recording this catalyst P d content is 0.035%, and Ag content is 0.2%, and Mg content is 0.1%, and the total metal dispersity of Pd and Ag is 12%.
With hydrogenating materials and the hydroconversion condition identical with embodiment 1.React 800 hours results referring to table 2.
Three sections isothermal bed bioreactors of table 2 are average result after reaction in 800 hours
Find out that from embodiment 1 under same reaction conditions, adopt processing method of the present invention, its reactive activity and selectivity all are better than traditional method.
Catalyzer adopts method preparation of the present invention.
Taking by weighing length is 4.5mm, and specific surface area is 2m
2/ g, pore volume are 0.18ml/g, and bulk density is 1.2g/cm
3Garden cylindricality Al
2O
3Carrier 500g.
Take by weighing 0.19g Pd (NO again
3)
22H
2O, 5.27g Mg (NO
3)
26H
2O and 5.7g urea are dissolved in and are mixed with mixing solutions in the deionized water, and the volume of solution is 90ml.With Al
2O
3In the carrier input mixing solutions solution is absorbed, then it is moved in container, react 24h under 80 ℃ of temperature, solid particulate is taken out in the cooling back, uses the deionized water thorough washing, and is dry under 120 ℃, obtains PdMgAl-CO
3-LDHs/Al
2O
3Presoma.
Take by weighing 0.86g AgNO
3, 2.2g NaSCN prepares Ag (CNS)
2 -The title complex solion, its volume 81ml, the pH value is 3.With PdMgAl-CO
3-LDHs/Al
2O
3Presoma drops in the title complex solion of above-mentioned Ag, and in react 24h under 80 ℃ of temperature, solid particulate is taken out in the cooling back, uses the deionized water thorough washing, and is dry under 110 ℃, obtains PdMgAl-Ag (CNS)
2-LDHs/Al
2O
3Presoma.
With PdMgAl-Ag (CNS)
2-LDHs/Al
2O
3Presoma is at 600 ℃ of roasting temperature 2h, makes PdMgAl-Ag (CNS)
2-LDHs/Al
2O
3Change corresponding complex metal oxides into; Be positioned over before the use in the fixed-bed reactor, use H
2100 ℃ of temperature, 4h is handled in reduction, obtains high-dispersion loading type palladium-silver catalyst.
Method according to embodiment 1 prepares catalyzer, and recording this catalyst P d content is 0.015%, and Ag content is 0.11%, and Mg content is 0.1%.The total metal dispersity of Pd and Ag is 70%.
Reaction mass: from deethanizer overhead, raw material is formed as table 3.
Table 3 hydrogenating materials is formed
| Hydrogenating materials | H 2 | C 2H 2 | C 2H 4 | C 2H 6 | CH 4 | CO |
| Content (V%) | 32 | 1.1 | 44 | 7.5 | 15.2 | 0.02 |
1: two section isothermal bed bioreactor of reaction conditions; Single hop reactor content volume space velocity: 25000h
-1, working pressure: 3.5MPa, each section reactor catalyst loadings: 800ml;
2: two sections isothermal bed bioreactors of reaction conditions; Single hop reactor content volume space velocity: 6000h
-1, working pressure: 4.0MPa, each section reactor catalyst loadings: 800ml;
Comparative Examples 2:
Method according to patent US 4484015 embodiment 1 prepares catalyzer.
Taking by weighing length is 4.5mm, and specific surface area is 2m
2/ g, pore volume are 0.18ml/g, and bulk density is 1.2g/cm
3Garden cylindricality Al
2O
3Carrier 500g.
Take by weighing 0.19g Pd (NO
3)
22H
2O is dissolved in the 90ml deionized water, is 3.5 with the pH value of dilute hydrochloric acid regulator solution, and described carrier impregnation in the solution that has prepared, 120 ℃ of dryings 10 hours, is obtained catalyst A, and 90% Pd is distributed in the scope of surperficial 300um in this catalyzer.
Take by weighing 5.27g Mg (NO again
3)
26H
2O, 0.86gAgNO
3, be dissolved in the 90ml deionized water, be 4.0 with the pH value of rare nitric acid regulator solution, described catalyst A is immersed in the solution that has prepared, 120 ℃ of dryings 10 hours,, use H 450 ℃ of roastings 8 hours
2100 ℃ of temperature, 4h is handled in reduction, obtains load type palladium-silver catalyst.
Record that Pd content is 0.015% in this catalyzer, Ag content is 0.11%, and Mg content is 0.1%, and the total metal dispersity of Pd and Ag is 12%.
With hydrogenating materials and the hydroconversion condition identical with embodiment 2.Reacted result such as table 4 and table 5 1000 hours.
Table 4 uses reaction conditions reaction in 1,1000 hour average result
Table 5 used reaction conditions 2, through 1000 hours reaction average results
Find out that from table 4,5 under same reaction conditions, adopt processing method of the present invention, its reactive activity and selectivity all are better than traditional method.When the reaction raw materials volume space velocity drops to 5000h
-1The time, adopt method of the present invention, reaction can normally be carried out, and temperature runaway then takes place in traditional method easily.
Taking by weighing diameter of section is 2.2mm, and length is 5～10mm, and specific surface area is 20m
2/ g, pore volume are 0.25ml/g, and bulk density is 0.8g/cm
3Bar shaped Al
2O
3500g.
Take by weighing 0.62g Pd (NO again
3)
22H
2O, 5.27g Mg (NO
3)
26H
2O, 5.2g urea are dissolved in and are mixed with mixing solutions in the deionized water, and the volume of solution is 150ml.With Al
2O
3In the carrier input mixing solutions solution is absorbed, then it is moved in container, react 8h under 160 ℃ of temperature, solid particulate is taken out in the cooling back, uses the deionized water thorough washing, and is dry under 120 ℃, obtains PdMgAl-CO
3-LDHs/Al
2O
3Presoma.
Take by weighing 0.16g AgNO
3, 2.2g NaSCN prepares Ag (CNS)
2 -The title complex solion, its volume 120ml, the pH value is 4.5.With PdMgAl-CO
3-LDHs/Al
2O
3Presoma drops in the title complex solion of above-mentioned Ag, and in react 10h under 120 ℃ of temperature, solid particulate is taken out in the cooling back, uses the deionized water thorough washing, and is dry under 110 ℃, obtains PdMgAl-Ag (CNS)
2-LDHs/Al
2O
3Presoma.
With PdMgAl-Ag (CNS)
2-LDHs/Al
2O
3Presoma is at 250 ℃ of roasting temperature 24h, makes PdMgAl-Ag (CNS)
2-LDHs/Al
2O
3Change corresponding complex metal oxides into; Be positioned over before the use in the fixed-bed reactor, use H
2100 ℃ of temperature, 4h is handled in reduction, obtains high-dispersion loading type palladium-silver catalyst.
Recording this catalyst P d content is 0.05%, and Ag content is 0.02%, and Mg content is 0.1%, and the total metal dispersity of Pd and Ag is 40%.
Hydrogenating materials is formed as table 6 from deethanizing column.
Table 6 hydrogenating materials is formed
| Hydrogenating materials | H 2 | C 2H 2 | C 2H 4 | C 2H 6 | CH 4 | CO | C 4 + |
| Content (V%) | 25 | 0.8 | 40 | 5.88 | 30 | 0.02 | 0.3 |
Reaction process condition 1: front-end deethanization front-end hydrogenation technology, two sections adiabatic reactors; Single hop reactor content volume space velocity: 5000h
-1Working pressure: 4.5MPa, single reactor loaded catalyst: 800ml.
Reaction process condition 2: front-end deethanization front-end hydrogenation technology, two sections adiabatic reactors; Single hop reactor content volume space velocity: 20000h
-1Working pressure: 3.5MPa, single reactor loaded catalyst: 200ml.
Comparative Examples 3
Method according to patent US 4404124 embodiment 1 prepares catalyzer, takes by weighing Al
2O
3Carrier 500g, its specific surface area is 20m
2/ g; Pore volume is 0.25ml/g; Bulk density is 0.8g/cm
3
Take by weighing 0.62g Pd (NO
3)
22H
2O is dissolved in the 150ml deionized water.
In the above-mentioned solution behind the 1h, inclining raffinate, at 120 ℃ of dry 3h, obtains catalyst A with carrier impregnation.
Take by weighing 5.27g Mg (NO
3)
26H
2O, 0.16g AgNO
3, be dissolved in the 225ml deionized water, be 2.5 with rare nitre acid for adjusting pH value.Above-mentioned catalyst A be impregnated in the solution that has prepared, place the vibration still, behind the vibration 30min, take out at 120 ℃ of dry 2h, this presoma obtains composite oxides at 500 ℃ of roasting temperature 8h.
Described composite oxides are positioned in the fixed-bed reactor before use, are N with mol ratio
2: H
2=0.1: 1 mixed gas, 120 ℃ of temperature, 12h is handled in reduction, obtains going back ortho states palladium-silver catalyst.
Recording this catalyst P d content is 0.05%, and Ag content is 0.02%, and Mg content is 0.1%, and the total metal dispersity of Pd and Ag is 5.2%.
With hydrogenating materials and the hydroconversion condition identical with embodiment 3.Result such as table 7 and table 8.
Table 7 used reaction conditions 1, through 1000 hours reaction average results
Table 8 used reaction conditions 2, through 1000 hours reaction average results
From above embodiment as can be seen, adopt method of the present invention after, the selectivity of C-2-fraction hydrogenation reaction increases substantially.Just because of the raising of reaction preference, make reaction in the adiabatic reactor reactor, to carry out.Thereby can reduce the energy consumption of process significantly, greatly facilitate operation.And be not easy to take place temperature runaway, the security of reaction system is improved greatly, improved the economic benefit of device.
Claims (10)
1. the selection method of hydrotreating of a C-2-fraction, adopt the front-end hydrogenation processing method of front-end deethanization, select hydrogenation with entering fixed-bed reactor from the overhead product of front-end deethanization tower in the ethylene unit, to remove alkynes wherein, it is characterized in that being equipped with in the fixed-bed reactor Pd-Ag series catalysts, the Pd-Ag series catalysts is meant with Al
2O
3Being carrier, is 100% in the quality of catalyzer, wherein contains Pd amount 0.01～0.1%; Containing Ag amount is 0.01～0.2%, adopts the hydroxide titration method to measure that total metal dispersity of Pd and Ag is 35～70% in the catalyzer, and catalyzer is to use introduces with the form of layered composite metal hydroxides that the method for Pd, Ag obtains; Reaction conditions is: 55～100 ℃ of reactor inlet temperatures, reaction pressure 2.5～4.5MPa, gas volume air speed 5000～25000h
-1
2. selection method of hydrotreating according to claim 1, the total metal dispersity that it is characterized in that Pd and Ag is 40～70%.
3. selection method of hydrotreating according to claim 1, when it is characterized in that fixed-bed reactor are the isothermal bed bioreactor, reactor inlet temperature is 60～100 ℃, and reaction pressure is 3.5～4.5MPa, and single bed bioreactor gas volume air speed is 6000～25000h
-1
4. selection method of hydrotreating according to claim 1, when it is characterized in that fixed-bed reactor are the adiabatic reactor reactor, reactor inlet temperature is 55～90 ℃, and reaction pressure is 2.5～3.5MPa, and single bed bioreactor gas volume air speed is 5000～20000h
-1
5. selection method of hydrotreating according to claim 1, the specific surface area that it is characterized in that catalyzer is 2～20m
2/ g; Pore volume is 0.2～0.5ml/g; Bulk density is 0.8～1.2g/cm
3
6. according to the arbitrary described selection method of hydrotreating of claim 1 to 5, it is characterized in that catalyzer is to prepare PdMgAl-CO earlier
3-LDHs/Al
2O
3Presoma prepares PdMgAl-Ag (complex)-LDHs/Al then
2O
3Presoma is again with PdMgAl-Ag (the complex)-LDHs/Al for preparing
2O
3The presoma roasting makes.
7. selection method of hydrotreating according to claim 6 is characterized in that catalyzer is to use following method to obtain:
A.PdMgAl-CO
3-LDHs/Al
2O
3The preparation of presoma
Palladium salt, magnesium salts and solubility organic amine be dissolved in be mixed with mixing solutions in the deionized water, its volume is Al
2O
380～120% of carrier pore volume is with Al
2O
3Carrier drops in the mixing solutions solution is absorbed, and reacts 5～24h under 80～200 ℃ of temperature, and solid particulate is taken out in the cooling back, uses the deionized water thorough washing, and is dry under 80～120 ℃, obtains PdMgAl-CO
3-LDHs/Al
2O
3Presoma;
B.PdMgAl-Ag (complex)-LDHs/Al
2O
3The preparation of presoma
The title complex solion of preparation Ag, its volume is PdMgAl-CO
3-LDHs/Al
2O
380～120% of the pore volume of presoma, and adjusting pH value is 3～6;
With PdMgAl-CO
3-LDHs/Al
2O
3Presoma drops in the title complex solion of above-mentioned Ag, reacts 5～24h under 80～150 ℃ of temperature, and solid particulate is taken out in the cooling back, uses the deionized water thorough washing, and is dry under 80～120 ℃, obtains PdMgAl-Ag (complex)-LDHs/Al
2O
3Presoma;
C. Preparation of catalysts
PdMgAl-Ag (complex)-LDHs/Al with step B preparation
2O
3Presoma makes PdMgAl-Ag (complex)-LDHs change corresponding complex metal oxides into, be catalyzer at 250～600 ℃ of roasting temperature 2～24h.
8. selection method of hydrotreating according to claim 7 is characterized in that palladium salt is Pd (NO
3)
22H
2O or PdCl
2Magnesium salts is Mg (NO
3)
26H
2O, MgCl
26H
2O or MgSO
47H
2O.
9. selection method of hydrotreating according to claim 7 is characterized in that the solubility organic amine is urea or hexamethylenetetramine.
10. selection method of hydrotreating according to claim 7, the title complex ion that it is characterized in that Ag are Ag (SCN)
2 -, Ag (EDTA)
3-Or Ag (S
2SO
3)
2-
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| CN102206130A (en) * | 2011-04-07 | 2011-10-05 | 中国石油天然气股份有限公司 | Selective hydrogenation method of C2 fraction |
| CN104415751A (en) * | 2013-08-27 | 2015-03-18 | 中国石油化工股份有限公司 | C2 fraction gas-phase selective hydrogenation catalyst and preparation method and application thereof |
| CN106590745A (en) * | 2015-10-20 | 2017-04-26 | 中国石油化工股份有限公司 | Selective front-end hydrogenation method for alkynes and/or dienes in C-2-fractions and C-3-fractions |
| CN106928000A (en) * | 2015-12-31 | 2017-07-07 | 中国石油天然气股份有限公司 | A kind of front-end deethanization front-end hydrogenation technique except alkynes method |
| CN115178262A (en) * | 2021-04-07 | 2022-10-14 | 中国石油化工股份有限公司 | Preparation method and application of C2 catalyst and C2 catalyst |
| CN115178261A (en) * | 2021-04-07 | 2022-10-14 | 中国石油化工股份有限公司 | C2 hydrogenation catalyst, preparation method and application thereof |
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|---|---|---|---|---|
| CN102206130A (en) * | 2011-04-07 | 2011-10-05 | 中国石油天然气股份有限公司 | Selective hydrogenation method of C2 fraction |
| CN102206130B (en) * | 2011-04-07 | 2013-10-16 | 中国石油天然气股份有限公司 | Selective hydrogenation method of C2 fraction |
| CN104415751A (en) * | 2013-08-27 | 2015-03-18 | 中国石油化工股份有限公司 | C2 fraction gas-phase selective hydrogenation catalyst and preparation method and application thereof |
| CN106590745A (en) * | 2015-10-20 | 2017-04-26 | 中国石油化工股份有限公司 | Selective front-end hydrogenation method for alkynes and/or dienes in C-2-fractions and C-3-fractions |
| CN106590745B (en) * | 2015-10-20 | 2018-03-02 | 中国石油化工股份有限公司 | A kind of selection front-end hydrogenation method of alkynes and/or alkadienes in carbon two, C3 fraction |
| CN106928000A (en) * | 2015-12-31 | 2017-07-07 | 中国石油天然气股份有限公司 | A kind of front-end deethanization front-end hydrogenation technique except alkynes method |
| CN106928000B (en) * | 2015-12-31 | 2019-09-03 | 中国石油天然气股份有限公司 | A kind of front-end deethanization front-end hydrogenation technique removes alkynes method |
| CN115178262A (en) * | 2021-04-07 | 2022-10-14 | 中国石油化工股份有限公司 | Preparation method and application of C2 catalyst and C2 catalyst |
| CN115178261A (en) * | 2021-04-07 | 2022-10-14 | 中国石油化工股份有限公司 | C2 hydrogenation catalyst, preparation method and application thereof |
| CN115178262B (en) * | 2021-04-07 | 2023-04-18 | 中国石油化工股份有限公司 | Preparation method and application of C2 catalyst and C2 catalyst |
| CN115178261B (en) * | 2021-04-07 | 2023-04-18 | 中国石油化工股份有限公司 | C2 hydrogenation catalyst, preparation method and application thereof |
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