CN101913975B - Selective hydrogenation method for C2 distillate - Google Patents
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- CN101913975B CN101913975B CN2009100920845A CN200910092084A CN101913975B CN 101913975 B CN101913975 B CN 101913975B CN 2009100920845 A CN2009100920845 A CN 2009100920845A CN 200910092084 A CN200910092084 A CN 200910092084A CN 101913975 B CN101913975 B CN 101913975B
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Abstract
The invention discloses a selective hydrogenation method for C2 distillate. The method is characterized in that: the reaction conditions comprise that: the inlet temperature of a reactor is 25 to 90 DEG C, the reaction pressure is 1.5 to 2.5MPa, the gaseous hourly space velocity of the single-stage reactor is 2,000 to 12,000/h, and the ratio of hydrogen to acetylene is 0.6-4:1; the catalyst carrier is an Al2O3 carrier and contains 0.03 to 0.05 percent of Pd and 0.05 to 0.20 percent of Ag based on 100 percent of the mass of the catalyst; and measured by adopting a hydrogen-oxygen titration method, the total metal dispersion degree of the Pd and the Ag in the catalyst is 30 to 70 percent. The method greatly reduces the generation amount of green oil, reduces the surface coking amount of the catalyst, prolongs the service life of the catalyst, improves the stability of process operation, and also can improve the increment of ethylene so as to improve the economic benefit of a device.
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
Polymer grade ethylene production is the tap of petrochemical industry, and polymer grade ethylene and propylene are the basic raw materials of downstream poly-unit, and the divinyl in the C-4-fraction is elastomeric main raw material.Other heavy component in the steam cracking product then is the important source material of petrochemical complex.Wherein the selection hydrogenation of acetylene has extremely important influence to the ethene processing industry, 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, to improving the yield of ethene of whole technological process, it is significant to improve the device economic benefit.
It is 0.5%～2.5% acetylene that the cracking C-2-fraction contains molar fraction, when producing polyethylene, a little acetylene in the ethene can reduce the activity of polymerizing catalyst, and make the deterioration in physical properties of polymkeric substance, so the acetylene content in the ethene must be dropped to certain limit, could be as the monomer of synthetic high polymer.Therefore acetylene separation and conversion are one of processes important in the ethylene unit flow process.The acetylene that removes in the splitting gas in the ethylene unit mainly adopts two class processing methodes at present, and promptly extracting rectifying and catalysis selective hydrogenation transform.
Solvent extraction rectifying separation acetylene is to adopt solvent (as dimethyl formamide, N-Methyl pyrrolidone, acetone etc.) extracting and separating acetylene, both removed the acetylene in the splitting gas, again with acetylene as a kind of useful products utilization, this technology has coproduction economic benefit preferably, but this flow operations is strict, complex process, therefore contaminate environment adopts the full scale plant of this flow process less.Solvent extraction rectifying relatively, it is ethene that catalysis selective hydrogenation makes acetylene conversion, improves ethylene content, is present most economical operational path, is widely used at home and abroad.
Catalysis selective hydrogenation is divided into front-end hydrogenation and back end hydrogenation according to acetylene hydrogenation reactor with respect to the demethanizing tower position in the ethylene unit, hydrogenator is a front-end hydrogenation before being positioned at demethanizing tower, hydrogenator is a back end hydrogenation after being positioned at demethanizing tower, is called sequence flow technology again.Concrete technology is: splitting gas is through washing, oil wash, after the alkali cleaning, at first pass through demethanizing tower, its cat head is carbon one cut and hydrogen, from carbon two and the C3 fraction that the tower still is drawn, passes through deethanizing column again, separate carbon two and C3 fraction, the composition of its cat head is C-2-fraction, also is hydrogenating materials, and its most of composition is an ethene, all the other are a spot of ethane, acetylene, C-2-fraction enter fixedly the adiabatic reactor reactor to carry out gas phase hydrogenation and removes acetylene, and ethene is 65～85% (V/V) in the reactor inlet raw material), ethane 10～20% (V/V)), acetylene is 1.0～2.5% (V/V)).The advantage of back end hydrogenation technology is that the hydrogenation process control device is many, is difficult for temperature runaway, and is easy to operate, but the shortcoming easy coking that is catalyzer, the reproduction ratio of catalyzer is more frequent.Its reason is in hydrogenation process, because the amount of allocating into of hydrogen is few, the hydrogenation dimerization reaction of acetylene takes place easily, generates 1,3-butadiene, and further generates the oligopolymer of molecular weight broad, is commonly called as " green oil ".Green oil is adsorbed on catalyst surface, and further forms coking, blocks the catalyzer duct, and catalyst activity and selectivity are descended.
Carbon current two back end hydrogenations mainly adopt two sections or three sections reactors in series technologies, and the device that air speed is lower or alkynes content is low can adopt the two reactor series connection.Present full scale plant is mainly based on three sections reactors in series technologies.
(Chem.Commun. such as Park, 1991, B1188-1189 and Ind.Eng.Chem.Res., 1992,31:469-474) load on palladium on the aluminum oxide and add the surface acidity that basic metal potassium and/or alkaline earth metals calcium, magnesium etc. are regulated alumina supporter or catalyzer, improve ethylene selectivity, reduced green oil generating amount, prolonged the cycle of operation.US 5856262 has reported that the silicon oxide with potassium hydroxide (or oxyhydroxide of barium, strontium, rubidium etc.) modification is a carrier, and the method for the low acid palladium catalyst of preparation is at air speed 3000h
-1, 35 ℃ of temperature ins, inlet acetylene molar fraction 0.71%, under the condition of hydrogen alkynes mol ratio 1.43, outlet acetylene molar fraction is less than 1 * 10
-7, ethylene selectivity reaches 56%.Patent US 4404124 is a carrier with the aluminum oxide, adds promotor silver and palladium effect, has prepared carbon two hydrogenation catalysts of excellent property.This catalyzer has the ethane of minimizing growing amount, and the acetylene that suppresses to be adsorbed on the catalyst surface carries out the partial hydrogenation dimerization reaction, suppresses 1, the 3-divinyl generates, and reduces green oil and generates, and improves ethylene selectivity, reduce the characteristics of oxygenatedchemicals growing amount, in ethylene industry, obtained widespread use.Yet above-mentioned catalyzer all is to adopt immersion process for preparing, is subjected to preparation method's restriction, and metal dispersity only is about 30%, and also there are many deficiencies in catalyst performance, and further improved necessity is still arranged.
Traditional hydrogenation catalyst all is to adopt immersion process for preparing, is subjected to the influence of steeping fluid surface tension and solvation effect in the dipping of catalyzer and drying treatment process, 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.More than the generation of two kinds of phenomenons cause the bad dispersibility of metal active constituent easily, and then have influence on the performance of catalyzer and the repeatability of preparation.Improve the dispersiveness of catalyst activity component,, improve the active ingredient utilization ratio, especially precious metal such as Pd, Pt etc. are had crucial meaning reducing the charge capacity of active ingredient.
Summary of the invention
The object of the present invention is to provide a kind of method of C-2-fraction back end hydrogenation, by selecting Pd, the Ag catalyzer of high degree of dispersion, the selectivity that improved hydrogenation has improved the increment of ethene, has improved the economic benefit of device operation.
The inventor finds, big grain surface has a plurality of active centre to exist in the catalyzer, two active centre are when nearer, the hydrogenation dimerization may take place in (acetylene) molecule that two triple bonds are opened, and generates 1,3-butadiene, therefore, improving dispersion degree of active components, increase the spacing in active centre, is the essential measure that reduces the hydrogenation dimerization reaction.
A kind of C 2 fraction selective hydrogenation method: with in the sequence flow technology from carbon two hydrogenation materials of deethanizing column, hydrogenation is selected in introducing fixedly adiabatic reactor reactor, it is characterized in that reaction conditions is: 20～90 ℃ of reactor inlet temperatures, reaction pressure 1.5～2.5MPa, single hop gas reactor volume space velocity 2000～12000h
-1, hydrogen/acetylene (V/V)=(0.6)～4: 1; Support of the catalyst is Al
2O
3Carrier is 100% in the quality of catalyzer, wherein contains Pd 0.01～0.1%, preferably 0.03～0.05%; Contain Ag 0.05～0.20%, adopt the hydroxide titration method to measure that total metal dispersity of Pd and Ag is 30～70% in the catalyzer, preferably 35～65%; Reactor is more than one section or two sections.The specific surface area of catalyzer is preferably 10～100m
2/ g, particularly 15～50m
2/ g; Pore volume is preferably 0.2～0.6ml/g, particularly 0.3～0.5ml/g; Bulk density is preferably 0.5～1.0g/cm
3, 0.6～0.9g/cm particularly
3General first stage reactor inlet is C
2H
21.0～2.5% (V/V).
Bed to reactor among the present invention is not limited especially, according to the difference of alkynes content, can use the multistage insulation bed bioreactor more than two sections usually.
The back end hydrogenation raw material generally consists of: the acetylene of 1.0～2.5% (v/v), and 65～85% ethene (v/v), all the other are ethane, hydrogen is allocated into after measuring.
This reaction is for thermopositive reaction, but temperature rise is relatively low, and according to the air speed size, the single reactor maximum temperature rise does not wait from 30～60 ℃, so adopt adiabatic reactor substantially.
To two reactor, first section reactor requires to transform the acetylene more than 70%, second section reactor with remaining acetylene conversion to its content less than 5 * 10
-6% (V/V).
The device higher to air speed or acetylene content is higher generally adopts three sections reactor process, and first section transforms about 50%, and all the other two sections transform remaining acetylene, and three sections reactor outlet acetylene contents are less than 5 * 10
-6% (V/V).
The amount of allocating into of hydrogen is relevant with acetylene content and adopting process.
When reactor was two sections adiabatic reactors, best conditions was: the first stage reactor temperature in is 25～85 ℃, H
2/ C
2H
2(V/V) be 1～3: 1; Two sections temperature ins are 30～90 ℃, H
2/ C
2H
2(V/V) be 1.5～4: 1.
When reactor was three sections adiabatic reactors, best conditions was: the first stage reactor temperature in is 30～65 ℃, H
2/ C
2H
2(V/V) be 0.6～1.5: 1; Two sections temperature ins are 40～70 ℃, H
2/ C
2H
2(V/V) be 1～3: 1; 50～85 ℃ of three sections temperature ins, H
2/ C
2H
2Be 1.5～4: 1.
This Pd-Ag activity of such catalysts component dispersity is higher than traditional Pd-Ag catalyzer.Because catalyst activity component dispersity height, the utilization ratio height of active ingredient, the more important thing is, owing to improved dispersion degree of active components, spacing between the active centre widens, make the probability that the acetylene hydrogenation dimerization reaction takes place descend significantly, the selectivity of catalyst reaction and catalyst surface coking descend significantly, and the operation life of catalyzer prolongs.
This support of the catalyst is Al
2O
3Carrier, the specific surface area of catalyzer is preferably 10～50m
2/ g; Pore volume is preferably 0.2～0.5ml/g; Bulk density is preferably 0.5～0.9g/cm
3
Al
2O
3Carrier can be sphere, bar shaped, cloverleaf pattern, Herba Galii Bungei shape, or the tooth ball-type etc.Described Al
2O
3Carrier can also be to carry out modification through other element, as Si, Ti, Zr etc., the Al after the modification
2O
3Carrier does not influence enforcement of the present invention, and method of modifying commonly used all can.
The present invention has adopted novel high degree of dispersion Pd-Ag series catalysts, the dispersity of this catalyzer requires to reach more than 30%, the selectivity and the traditional catalyst of reaction have significant difference, the dispersity of activity of such catalysts component is improved largely than traditional catalyst, the dispersity of traditional catalyst is 10～20%, typically as G-58C etc.
Be not particularly limited the approach that employed catalyzer improves the active ingredient dispersity among the present invention, but preferably the most preferred scheme of the present invention adopts the catalyzer that synthetic layered composite metal hydroxides prepares.
Palladium-palladium-silver system supported catalyst will obtain so high metal dispersity, 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.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
390～110% 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 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
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.
Use procatalyst to be positioned in the reaction unit, use H
2Or contain H
2Mixed gas, 80～250 ℃ of temperature, obtain going back the ortho states catalyzer.
Used palladium salt 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 can reach 30～45% usually, in addition higher.Adopt the Pd-Ag/Al of traditional immersion process for preparing
2O
3Sample, recording its dispersity with aforesaid method only is about 20%.
The inventor finds that when the catalyzer that adopts this active ingredient high dispersive carried out hydrogenation reaction, green oil generating amount reduced greatly, and the catalyst surface coking amount is low.Have by a relatively large margin than traditional catalyst the work-ing life of catalyzer to prolong, improve the stability of technological operation greatly.Because selectivity of catalyst improves, can improve the increment of ethene, and then improve the economic benefit of device.
Description of drawings
Fig. 1 is carbon two back end hydrogenation process flow sheets.
Among the figure: the 1-oil scrubber; The 2-water wash column; The 3-soda-wash tower; The 4-moisture eliminator; The 5-demethanizing tower; The 6-deethanizing column; 7-carbon two hydrogenators; The 8-interchanger.
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.
Selectivity=1-|[Δ ethane/Δ acetylene] |
Preparation of Catalyst:
Take by weighing Al
2O
3Carrier 500g, its specific surface area is 10m
2/ g; Pore volume is 0.2ml/g; Bulk density is 0.9g/cm
3
Take by weighing 0.44g Pd (NO again
3)
22H
2O, 12.12g Mg (NO
3)
26H
2O and 5g hexamethylenetetramine are dissolved in and are mixed with mixing solutions in the deionized water, and the volume of solution is 100ml.With spherical Al
2O
3Carrier drops in the mixing solutions solution is absorbed, and then it is moved in the container, reacts 5h under 200 ℃ of temperature, and 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 0.55g AgNO
3With 0.13g NaSCN preparation Ag (CNS)
2 -The title complex solion, its volume 100ml, and be 6 with rare nitre acid for adjusting pH value.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 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
2120 ℃ of temperature, 6h 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 0.07%, and Mg content is 0.23%, and the total metal dispersity of Pd and Ag is 35%.
Reaction raw materials is from the deethanizing column of sequence flow, and raw material consists of:
C
2H
2：1.0％(V％)C
2H
480％(V％)，C
2H
619％(V％)
Reaction conditions:
Single hop is the adiabatic reactor reactor fixedly, volume of material air speed: 2000h
-1, working pressure: 1.0MPa, loaded catalyst: 300ml.25 ℃ of reactor inlet temperatures, H
2/ C
2H
2=0.8: 1 (V/V).
Comparative Examples 1
Adopt the method for the embodiment 1 of US4404124 to prepare catalyzer.
Take by weighing Al
2O
3Carrier 500g, its specific surface area is 10m
2/ g; Pore volume is 0.2ml/g; Bulk density is 0.9g/cm
3
Take by weighing 0.44g Pd (NO
3)
22H
2O is dissolved in the 435ml 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 12.12g Mg (NO
3)
26H
2O, 0.55g AgNO
3, be dissolved in the 100ml deionized water, be 6 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 600 ℃ of roasting temperature 2h.
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 0.035%, and Ag content is 0.7%, and Mg content is 0.23%, and the total metal dispersity of Pd and Ag is 12%.
Raw material composition and reaction conditions are with embodiment 1.Average result is as shown in table 1 after reaction in 500 hours.
Table 1500 hour hydrogenation reaction result
| Project | Temperature in ℃ | Temperature rise ℃ | C 2H 2Residual volume, v/v% | Hydrogenation selectivity, |
| Embodiment | ||||
| 1 | 25 | 58 | 0.02 | 88 |
| Comparative Examples 1 | 25 | 40 | 0.22 | 22 |
Can find out that by embodiment 1 and Comparative Examples 1 adopt method of hydrotreating of the present invention, the selectivity of its reaction and activity all are better than traditional method of hydrotreating.
Preparation of Catalyst: take by weighing Al
2O
3Carrier 500g, its specific surface area is 50m
2/ g; Pore volume is 0.5ml/g; Bulk density is 0.7g/cm
3
Take by weighing 0.63g Pd (NO
3)
22H
2O, 6.6g Mg (NO
3)
26H
2O and 5.5g urea are dissolved in and are mixed with mixing solutions in the deionized water, and the volume of solution is 200ml.With spherical Al
2O
3Carrier drops in the mixing solutions solution all is absorbed, and then it is moved in the container, reacts 10h under 180 ℃ of temperature, and 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 0.79g AgNO again
3With 0.25g NaSCN, preparation Ag (CNS)
2 -The title complex solion, its volume 235ml, and be 3 with rare nitre acid for adjusting pH value.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 550 ℃ of roasting temperature 4h, 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, 8h 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 0.10%, and Mg content is 0.13%.The total metal dispersity of Pd and Ag is 65%.
Reaction raw materials is from deethanizing column, and two reactor is connected, and promptly the first stage reactor outlet material enters second stage reactor.Every section reactor all has independently gas distributing system.
Every section reactor content volume space velocity: 2000h
-1, working pressure: 2.9MPa, every section reactor catalyst loadings: 300ml.25 ℃ of first stage reactor temperature ins,
H
2/ C
2H
2=1: 1 (V/V); 30 ℃ of second stage reactor temperature ins, H
2/ C
2H
2=1.5: 1 (V/V).
Reaction raw materials is formed: C
2H
22.5% (V%) C
2H
480% (V%), C
2H
618.5% (V%).
Every section reactor content volume space velocity: 12000h
-1, working pressure: 2.9MPa, every section reactor catalyst loadings: 300ml.85 ℃ of first stage reactor temperature ins,
H
2/ C
2H
2=3: 1 (V/V); 90 ℃ of second stage reactor temperature ins, H
2/ C
2H
2=4: 1 (V/V).
Reaction raw materials is formed: C
2H
21.0% (V%) C
2H
480% (V%), C
2H
618.5% (V%).
Comparative Examples 2
Take by weighing Al
2O
3Carrier 500g, its specific surface area is 60m
2/ g; Pore volume is 0.5ml/g; Bulk density is 0.7g/cm
3
Take by weighing 0.63g Pd (NO again
3)
22H
2O, 0.79g AgNO
3, be dissolved in the 200ml deionized water, be 3 with rare nitric acid regulator solution pH value, the solution spraying for preparing to above-mentioned carrier, 120 ℃ of dryings 3 hours, is called catalyst A, stand-by.
Take by weighing 6.6g Mg (NO again
3)
26H
2O is dissolved in the 265ml deionized water, is 2.5 with rare nitric acid regulator solution pH value, catalyst A is dissolved in the solution for preparing, 120 ℃ of dryings 3 hours.
At 550 ℃ of roasting temperature 4h, corresponding metal salt changes corresponding complex metal oxides into; Be positioned over before the use in the fixed-bed reactor, use H
2100 ℃ of temperature, 8h is handled in reduction, obtains load type palladium-silver catalyst.
Recording this catalyst P d content is 0.05%, and Ag content is 0.10%, and Mg content is 0.13%.The total metal dispersity of Pd and Ag is 9%.
With hydrogenating materials and the hydroconversion condition identical with embodiment 2.Average result is shown in table 2 and table 3 after reaction in 1000 hours.
Average result after 1 1000 hours hydrogenation reactions of table 2 reaction conditions
Average result after 2 1000 hours hydrogenation reactions of table 3 reaction conditions
Can find out that from embodiment 2 and Comparative Examples 2 when low-speed and Gao Qing/alkynes, when adopting method of hydrotreating of the present invention, the selectivity of reaction still remains on higher level, is much better than traditional method of hydrotreating.
Take by weighing Al
2O
3Carrier 500g, Al in the carrier
2O
3480g, TiO
220g, this carrier specific surface area is 35m
2/ g; Pore volume is 0.39ml/g; Bulk density is 0.78g/cm
3
Take by weighing 0.24g Pd (NO
3)
22H
2O, 8.4g Mg (NO
3)
26H
2O and 7.6g hexamethylenetetramine are dissolved in and are mixed with mixing solutions in the deionized water, and the volume of solution is 240ml.With Al
2O
3Carrier drops in the mixing solutions solution is absorbed, and then it is moved in the container, reacts 24h under 80 ℃ of temperature, and 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 1.58g AgNO again
3, 0.25g NaSCN, preparation Ag (CNS)
2 -The title complex solion, its volume 180ml, and be 5 with rare nitre acid for adjusting pH value.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, 8h is handled in reduction, and obtaining high-dispersion loading type palladium-silver catalyst, to record this catalyst P d content be 0.02%, and Ag content is 0.2%, and Mg content is 0.16%.The total metal dispersity of Pd and Ag is 70%.
Reaction raw materials is from the deethanizing column of sequence flow device.。
Reaction conditions: three sections adiabatic reactor reactors in series, promptly the first stage reactor outlet material enters second stage reactor after cooling, and the second stage reactor outlet material enters three sections reactors after cooling.Every section reactor all has independently gas distributing system.
Raw material consists of:
C
2H
2 2.5％(V％) C
2H
4 80％(V％)，C
2H
617.5％(V％)
C
2H
2：1.5％(V％) C
2H
4 80％(V％)，C
2H
617.5％(V％)
Comparative Examples 3
Take by weighing carrier 500g similarly to Example 3, this carrier specific surface area is 35m
2/ g; Pore volume is 0.39ml/g; Bulk density is 0.78g/cm
3
Take by weighing 0.24g Pd (NO again
3)
22H
2O, 1.78g AgNO
3, 8.4g Mg (NO
3)
26H
2O is dissolved in the 240ml aqueous solution, is 3.2 with rare nitric acid regulator solution pH value, and above carrier impregnation in the solution that has prepared, was rotated 30 minutes, 110 ℃ of dryings 2 hours, 500 ℃ of roastings 4 hours, obtains oxidized catalyst.Use H
2100 ℃ of temperature, 8h is handled in reduction, obtains load type palladium-silver catalyst.
Record Pd and get content 0.02%, Ag content is 0.2%, and Mg content is 0.16%.The total metal dispersity of Pd and Ag is 23%.
With hydrogenating materials and the hydroconversion condition identical with embodiment 3.500 hours hydrogenation reaction results such as table 4 are shown in the table 5.
Average result after 500 hours hydrogenation reactions of table 4 reaction conditions
Average result after 500 hours hydrogenation reactions of table 5
Can be found out by embodiment, adopt method of hydrotreating of the present invention, when system pressure was low, catalyzer also had good active.Hydrogen/alkynes is when being significantly less than present full scale plant data, and the coking degree of catalyzer obviously is less than present employed method of hydrotreating.Catalyst activity and selectivity are able to good maintenance, and especially reaction preference obviously is better than traditional method.
Claims (9)
1. C 2 fraction selective hydrogenation method, with in the sequence flow technology from carbon two hydrogenation materials of deethanizing column, hydrogenation is selected in introducing fixedly adiabatic reactor reactor, it is characterized in that reaction conditions is: 25～90 ℃ of reactor inlet temperatures, reaction pressure 1.5～2.5MPa, reactor is more than one section or two sections, single hop gas reactor volume space velocity 2000～12000h
-1, hydrogen/acetylene volume ratio is 0.6～4:1; Support of the catalyst is Al
2O
3Carrier is 100% in the quality of catalyzer, wherein contains Pd0.01～0.1%; Contain Ag0.05～0.20%, adopt the hydroxide titration method to measure that total metal dispersity of Pd and Ag is 30～70% in the catalyzer, catalyzer is to use introduces with the form of layered composite metal hydroxides that the method for Pd, Ag obtains; 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: 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 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
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 is at 250～600 ℃ of roasting temperature 2～24h, makes PdMgAl-Ag (complex)-LDHs/Al
2O
3Change corresponding complex metal oxides into, be catalyzer.
2. method according to claim 1 is characterized in that containing in the catalyzer Pd0.03～0.05%.
3. method according to claim 1, the dispersity that it is characterized in that Pd, Ag is 35～65%.
4. method according to claim 1, the specific surface area that it is characterized in that catalyzer is 10～100m
2/ g, pore volume are 0.2～0.6ml/g; Bulk density is 0.5～1.0g/cm
3
5. method according to claim 1 is characterized in that reactor is two sections adiabatic reactors, and wherein one section temperature in is 25～85 ℃, H
2/ C
2H
2(V/V) be 1～3:1; Two sections temperature ins are 30～90 ℃, H
2/ C
2H
2(V/V) be 1.5～4:1.
6. method according to claim 1 is characterized in that reactor is three sections adiabatic reactors, and wherein one section temperature in is 30～65 ℃, H
2/ C
2H
2(V/V) be 0.6～1.5:1; Two sections temperature ins are 40～70 ℃, H
2/ C
2H
2(V/V) be 1～3:1; 50～85 ℃ of three sections temperature ins, H
2/ C
2H
2(V/V) be 1.5～4:1.
7. method according to claim 6 is characterized in that Al
2O
3Carrier is through Si or Ti modification.
8. method according to claim 1 is characterized in that among the step B, the title complex solion of preparation Ag, and its volume is PdMgAl-CO
3-LDHs/Al
2O
390～110% of the pore volume of presoma, and adjusting pH value is 3.5～6.
9. method according to claim 1 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; The solubility organic amine is urea or hexamethylenetetramine; The title complex ion of Ag is Ag (SCN)
2 -, Ag (EDTA)
3-Or Ag (S
2SO
3)
-
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| CN102206131B (en) * | 2011-04-07 | 2013-12-04 | 中国石油天然气股份有限公司 | Selective hydrogenation method for 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 |
| EP2937141B1 (en) * | 2013-11-18 | 2020-01-01 | LG Chem, Ltd. | Method for preparing a molybdenum-bismuth-containing catalyst composition using a hydrotalcite binder, said catalyst composition and its use in oxidative dehydrogenation |
| CN103819298B (en) * | 2014-03-07 | 2015-09-02 | 中石化上海工程有限公司 | C-2-fraction selective hydrogenation method |
| CN105126914B (en) * | 2015-08-07 | 2018-09-07 | 北京华福工程有限公司 | A kind of high dispersive catalyst system and catalyzing and its preparation method and application |
| CN106928003B (en) * | 2015-12-31 | 2019-09-03 | 中国石油天然气股份有限公司 | A kind of two back end hydrogenation technique of carbon removes alkynes method |
| CN106928013B (en) * | 2015-12-31 | 2019-09-03 | 中国石油天然气股份有限公司 | A kind of acetylene hydrogenation method of MTO technology ethylene feed |
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| Ly-C2-02C2 选择加氢除炔催化剂的工业应用;赵育榕;《工业催化》;20040731;第12卷(第7期);第18页 * |
| 赵育榕.Ly-C2-02C2 选择加氢除炔催化剂的工业应用.《工业催化》.2004,第12卷(第7期),第18页. |
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