CN102126908A - Method for performing selective hydrogenation on carbon2 (C2) fraction - Google Patents
Method for performing selective hydrogenation on carbon2 (C2) fraction Download PDFInfo
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- CN102126908A CN102126908A CN2010105802087A CN201010580208A CN102126908A CN 102126908 A CN102126908 A CN 102126908A CN 2010105802087 A CN2010105802087 A CN 2010105802087A CN 201010580208 A CN201010580208 A CN 201010580208A CN 102126908 A CN102126908 A CN 102126908A
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- hydrogenator
- fraction
- bed catalytic
- polymerizing catalyst
- hydrogenation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention relates to a method for performing selective hydrogenation on a carbon2 (C2) fraction. The method comprises the following steps of: performing hydrogen coordination on the C2 fraction from a deethanizing tower in an ethane device; and introducing the C2 fraction into a fixed bed catalytic hydrogenation reactor to perform selective hydrogenation so as to remove acetylene, wherein the fixed bed catalytic hydrogenation reactor is a multi-stage fixed bed catalytic hydrogenation reactor. The method is characterized in that: in the multi-stage fixed bed catalytic hydrogenation reactor, the C2 fraction is subjected to a selective hydrogenation reaction and a polymerization reaction; and a polymerization catalyst is used and preferably is a ZSM-5/Al2O3 catalyst. After the polymerization reaction is added by the method, the quantity of carbon4 (C4) olefin is greatly reduced and the polluted degree of a second-stage or third-stage hydrogenation catalyst is greatly reduced.
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, polymer grade ethylene and propylene are the basic raw materials of downstream poly-unit, 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.
The cracking C-2-fraction contains the acetylene that molar fraction is 0.5%～2.5% (v/v), 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 with respect to the demethanizing tower position, is divided into front-end hydrogenation and back end hydrogenation according to acetylene hydrogenation reactor in the ethylene unit, and hydrogenator is front-end hydrogenation before being positioned at demethanizing tower, and hydrogenator is a back end hydrogenation after being positioned at demethanizing tower.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, and shortcoming is the easy coking of catalyzer, and the reproduction ratio of catalyzer is more frequent.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 distribution 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 to remove alkynes technology, and the device that air speed is lower or alkynes content is low can adopt the two reactor series connection.Full scale plant mainly removes alkynes technology based on three sections reactors in series at present.
The back end hydrogenation material generally consists of: the acetylene of 1.0～2.5% (v/v), and the ethene of 65～85% (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 the two-stage hydrogenation reactor, first section hydrogenator requires to transform the acetylene more than 70%, second section hydrogenator with remaining acetylene conversion to its content less than 5 μ l/l.
The device higher to air speed or acetylene content is higher generally adopts three sections hydrogenator technologies, and first section transforms about 50% acetylene, and all the other two sections transform remaining acetylene, and three sections hydrogenator outlet acetylene contents are less than 5 μ l/l.
The amount of allocating into of hydrogen is relevant with acetylene content and adopting process.To three sections hydrogenator technologies, general first section hydrogenator hydrogen/acetylene is that 0.8～1.2, second section hydrogenator hydrogen/acetylene is that the 1～1.5, three section hydrogenator hydrogen/acetylene (v/v) is 1.5～3.
To the two-stage hydrogenation reactor process, general first section hydrogenator hydrogen/acetylene is that 1～1.5, second section hydrogenator hydrogen/acetylene is 1.5～4.
In general, one section generation green oil the easiest at reactor, these green oil parts can continue polymerization, finally coking on one section catalyzer, a part of in addition green oil can enter the secondary hydrogenation reactor with material, in coking of secondary hydrogenation reactor or enrichment, cause the catalyst performance of secondary hydrogenation reactor to descend, for fear of the generation of this situation, full scale plant is provided with the green oil separating tank behind first section hydrogenator, and its mechanism is by behind the heat exchanger, green oil is because the reduction of temperature of charge, be deposited on the bottom of green oil jar, intermittently emit green oil, avoid its pollution the secondary hydrogenation reactor by the green oil pot bottom.
The inventor finds, this technology is effective to heavier green oil composition, but to generate in the reaction than light constituent, especially then effect is relatively poor for C-4-fraction, after these lighter components enter the secondary hydrogenation reactor, still can cause to have a strong impact on, even make catalyst performance descend more than 80% catalyst performance, thereby cause the catalyzer cycle of operation to shorten, ethylene product purity descends.
Summary of the invention
The contriver has proposed to solve the scheme of carbon two hydrogenation process catalyst performances decay, and this scheme especially is fit to the order separation process.
A kind of method of C 2 fraction selective hydrogenation, with in the ethylene unit from the C-2-fraction of deethanizing column, after joining hydrogen, enter the fixed-bed catalytic hydrogenator and select hydrogenation, to remove acetylene wherein, the fixed-bed catalytic hydrogenator is multi-stage fixed-bed catalytic hydrogenation reaction device, it is characterized in that between multi-stage fixed-bed catalytic hydrogenation reaction device, C-2-fraction also has polymerization process except that the selective hydrogenation reaction process takes place, used polymerizing catalyst, this polymerizing catalyst is preferably ZSM-5/Al
2O
3Catalyzer.
Used polymerizing catalyst among the present invention, the C 4 olefin that the leading portion hydrogenation reaction is produced carries out polymerization, generate the oligopolymer of carbon eight even higher carbon number, so that better C-4-fraction is separated, reduce the influence of C-4-fraction to the back segment hydrogenator from the material of leading portion reactor outlet.
ZSM-5/Al of the present invention
2O
3Catalyzer is that prior art adopts ordinary method to prepare, shown in CN200510008986 like that, molecular sieve, aluminum oxide, tackiness agent are added water kneading, moulding, roasting obtain.The silica alumina ratio of molecular sieve is preferably 5～200, and specific surface area is 200～500m
2/ g.
Preferably select the ZSM-5 molecular sieve in the polymerizing catalyst of the present invention for use, its consumption is preferred 10～90%, and more preferably 30～80%.
Preferably select Al in the polymerizing catalyst of the present invention for use
2O
3Specific surface area is 50～300m
2/ g, its consumption preferred 10～90%.More preferably 20～70%.
Tackiness agent is a general purpose adhesive of the prior art, as Mierocrystalline cellulose, and aluminium colloidal sol etc.
The roasting condition of polymerizing catalyst is preferably 400～600 ℃, and the time is 2～8 hours.
According to scheme of the present invention, with in the ethylene unit from the C-2-fraction of deethanizing column, after joining hydrogen, enter fixed bed catalytic reactor and select hydrogenation, to remove acetylene wherein, the fixed-bed catalytic hydrogenator is preferably the multistage hydrogenator, as be secondary hydrogenation reactor, three sections hydrogenators or more hydrogenator, between hydrogenator, use polymerization reactor or be seated in polymerizing catalyst in the hydrogenator or preceding dual mode uses simultaneously.
Concrete scheme of the present invention can be to a polymerization reactor is arranged between the interchanger at first section hydrogenator, if the situation of three sections hydrogenator technologies, can also behind first section or second section hydrogenator, be provided with separately behind polymerization reactor or the first section hydrogenator with behind second section hydrogenator polymerization reactor is set simultaneously, or do not establish polymerization reactor, but polymerizing catalyst is seated in first section or/and in second section hydrogenator, described polymerizing catalyst preferably is seated in the end of hydrogenator reaction bed.
During polymerization reactor among the present invention after polymerizing catalyst fills in hydrogenator, this polymerization reactor is generally between the interchanger behind hydrogenator and the reactor, C-4-fraction is reacted under comparatively high temps, post reaction mixture is separated through the green oil jar, to remove the heavier cut of generation.
The hydrogen alkynes that enters the leading portion hydrogenator is than unsuitable too high, and a large amount of excessive hydrogen can cause the selectivity of hydrogenation reaction to reduce, and also can accelerate polyreaction, and the amount of hydrogen is preferably lower than 0.6% (volume) in the polyreaction.
Other the concrete reaction conditions the present invention who is used for C 2 fraction selective hydrogenation is not specially limited, and is generally: 20～80 ℃ of fixed-bed catalytic hydrogenator temperature ins, reaction pressure 1.5～2.5MPa, gas volume air speed 2000～10000h
-1, C in first section reactor inlet material
2H
2Account for 1.0～2.5%.
The general condition of polymerization reactor or polyreaction is: 65 ℃～130 ℃ of temperature of reaction, and reaction pressure 1.5～2.5MPa, the gas volume air speed is 5000～40000h
-1, the present invention is not restriction especially also, can adjust according to the difference of the polymerizing catalyst that adopts.
The inventor finds, when adopting method of the present invention, the alkene polymerization reaction take place of C-4-fraction, because C-4-fraction is easier of the ZSM-5 molecular sieve adsorption, and carbon two components are difficult to be aggregated catalyzer absorption, under big air speed condition (＞2000/h), can avoid the polymerization of carbon two components, generate the material of larger molecular weight.And by after the polyreaction, the amount of C 4 olefin descends significantly, and two sections or three sections contaminated degree of hydrogenation catalyst alleviate greatly.
Description of drawings
Fig. 1 is for using a kind of carbon two back end hydrogenation process flow sheets of the present invention.Wherein: 1---oil scrubber; 2---water wash column; 3---soda-wash tower; 4---moisture eliminator; 5---demethanizing tower; 6---deethanizing column; 7---first section hydrogenator; 8---polymerization reactor; 9---the secondary hydrogenation reactor; 10---three sections hydrogenators.
Embodiment
Catalyzer source and main rerum natura:
The G-58C catalyzer of the southern chemical company of Germany, the catalyzer outward appearance is light grey ball, granularity is φ 2～5mm, active ingredient Pd, bulk density 0.75 ± 0.01g/ml, BET specific surface 35 ± 5m
2/ g, BET pore volume 0.32 ± 0.02cm
3/ g, intensity 〉=60N/ grain.
Sinopec research institute LY-C
2-O2 catalyzer, outward appearance are the taupe ball.Granularity is φ 2.5～4mm, active ingredient Pd, bulk density 0.72 ± 0.01g/ml, BET specific surface 50 ± 5m
2/ g, BET pore volume 0.38 ± 0.02cm
3/ g, intensity 〉=60N/ grain.
Molecular sieve B:ZSM-5, Catalyst Factory, Nankai Univ, silica alumina ratio 90, specific surface area 180m
2/ g.
Molecular sieve C:ZSM-5, Qingdao make profits permanent International Trading Company Ltd, silica alumina ratio 200,280m
2/ g.
Overall selectivity: S=(ethene increment/hydrogenator inlet acetylene content that the outlet of each section hydrogenator is total) * 100 volume %
Embodiment 1
Technical process as shown in Figure 1, different is to adopt two sections carbon two hydrogenation techniques, reaction conditions: adiabatic reactor, G-58C hydrogenation catalyst loadings 300ml, first section hydrogenator inlet acetylene content 2.1% (v/v), air speed 3000/h, pressure 1.5MPa, 120 ℃ of first section hydrogenator temperature outs.Polymerization reactor loaded catalyst 100ml, the polymerizing catalyst preparation process is as follows:
Synthesizing of 1 molecular sieve
Reagent: tetrapropylammonium hydroxide, Alfa company; Tetraethoxy (content 98wt.%, Aldrich company); The triisopropyl aluminum oxide, Aldrich company.
Get the 110g tetrapropylammonium hydroxide and be dissolved in the 900g deionized water, 59g triisopropyl aluminum oxide stirs half an hour down at 0 ℃, obtains clear soln.In this solution, add the 218g tetraethoxy, stirred 4 hours down, make the tetraethoxy complete hydrolysis at 200 ℃, 400 ℃ of heating under vacuum, the ethanol of generation is volatilized fully, in the supersaturated solution that obtains, refluxed 100 hours down at 70 ℃, stir speed (S.S.) is 100rpm, and centrifugation is carried out in resulting crystallization, uses deionized water wash 3 times, 120 ℃ of dried overnight, 550 ℃ of roastings 5 hours, obtain molecular sieve ZSM-5 molecular sieve-4 A, the silicon/aluminium of molecular sieve=32.
The preparation of 2 polymerizing catalysts
Get the molecular sieve-4 A 180g of above-mentioned preparation, and the 20g aluminum oxide (commercially available, specific surface 180m
2/ g), take by weighing the 2g Mierocrystalline cellulose, add water and mediate, and be extruded into strip, 450 ℃ of roastings 3 hours.Obtain polymerizing catalyst A.
As shown in Figure 1, polymerizing catalyst A 200mL is filled in first section polymerization reactor behind the hydrogenator.80 ℃ of polymerization reactor temperature ins, inlet acetylene content are first section hydrogenator outlet acetylene content, pressure 1.5MPa, air speed 9000/h.
Comparative Examples 1: except that not having polymerization reactor, all the other conditions are identical with embodiment 1.
The reaction result of table 1 Comparative Examples 1 and embodiment 1
Embodiment 2
Technical process as shown in Figure 1, adopt three sections carbon two hydrogenation techniques, reaction conditions: three sections carbon two hydrogenation techniques, adiabatic reactor, hydrogenation catalyst loadings 300ml, first section hydrogenator inlet acetylene content 1.7% (mol ratio), pressure 2.0MPa, air speed 4000/h, 90 ℃ of first section hydrogenator temperature outs.The reaction bed bottom of first section hydrogenator is filled with polymerizing catalyst 150ml.Other is provided with polymerization reactor, polymerizing catalyst loadings 100ml, be positioned at the secondary hydrogenation reactor after, before three sections hydrogenators.100 ℃ of this polymerization reactor temperature ins, inlet acetylene content are second section hydrogenator outlet acetylene content, pressure 2.0MPa, air speed 12000/h.
Polymerizing catalyst is by the method preparation of present embodiment.
The preparation of polymerizing catalyst:
Get commercially available molecular sieve B 140g, the 60g aluminum oxide takes by weighing the 2g Mierocrystalline cellulose, adds water and mediates, and be extruded into strip, 550 ℃ of roastings 6 hours.Obtain catalyst B.
Comparative Examples 2: except that not having addition polymerization section and polymerization reactor, all the other conditions are identical with embodiment 2.
The reaction result of table 2 Comparative Examples 2 and embodiment 2
Embodiment 3
Reaction conditions: two sections carbon two hydrogenation techniques, adiabatic reactor, hydrogenation catalyst loadings 500ml, first section hydrogenator inlet acetylene content 1.8% (mol ratio), air speed 2000/h, pressure 2.5MPa, 105 ℃ of first section hydrogenator temperature outs.Adopt the technical process shown in the accompanying drawing 1, different is not establish polymerization reactor in addition, but is filled with polymerizing catalyst in the reaction bed bottom of first section hydrogenator, loadings 100ml, and polymerizing catalyst is synthetic by the method for present embodiment.
The preparation of polymerizing catalyst
Get commercially available molecular sieve C 100g, silica alumina ratio 200,280m
2/ g, and the 100g aluminum oxide (commercially available, specific surface 180m
2/ g), take by weighing the 2g Mierocrystalline cellulose, add suitable quantity of water and mediate, and be extruded into strip, 600 ℃ of roastings 2 hours.Obtain polymerizing catalyst C.
Polymerizing catalyst C 200g is filled in the reaction bed bottom of first section hydrogenator.
Comparative Examples 3: do not add the polymerizing catalyst in first section hydrogenator, all the other conditions are identical with embodiment 3.
The reaction result of table 3 Comparative Examples 2 and embodiment 2
From above embodiment, Comparative Examples as can be seen, after adopting method of the present invention, reduce the rate of decay of two, three sections reactor catalyst performances greatly, make the removal effect of acetylene and overall selectivity that obvious lifting be arranged, increased substantially the economic benefit of hydrogenation process.
Claims (10)
1. the method for a C 2 fraction selective hydrogenation, with in the ethylene unit from the C-2-fraction of deethanizing column, after joining hydrogen, enter the fixed-bed catalytic hydrogenator and select hydrogenation, to remove acetylene wherein, the fixed-bed catalytic hydrogenator is multi-stage fixed-bed catalytic hydrogenation reaction device, it is characterized in that between multi-stage fixed-bed catalytic hydrogenation reaction device C-2-fraction also has polymerization process except that the selective hydrogenation reaction process takes place, used polymerizing catalyst.
2. method according to claim 1 is characterized in that this polymerizing catalyst is ZSM-5/Al
2O
3Catalyzer.
3. method according to claim 1, it is characterized in that first section hydrogenator in multi-stage fixed-bed catalytic hydrogenation reaction device be exported between the interchanger and/or the secondary hydrogenation reactor outlet to being provided with a polymerization reactor between the interchanger, wherein loaded polymerizing catalyst.
4. method according to claim 1 is characterized in that being filled with polymerizing catalyst at the first section hydrogenator that is arranged in multi-stage fixed-bed catalytic hydrogenation reaction device and/or the reaction bed bottom of first section hydrogenator.
5. method according to claim 1 is characterized in that 20～80 ℃ of fixed-bed catalytic hydrogenator temperature ins, reaction pressure 1.5～2.5MPa, gas volume air speed 2000～10000h
-1, C in first section reactor inlet material
2H
2Account for 1.0～2.5%.
6. method according to claim 1 is characterized in that the condition of polyreaction is: 65 ℃～130 ℃ of temperature of reaction, and reaction pressure 1.5～2.5MPa, the gas volume air speed is 5000～40000h
-1
7. method according to claim 2 is characterized in that the ZSM-5 molecular sieve accounts for 10～90% in the polymerizing catalyst.
8. method according to claim 2 is characterized in that polymerizing catalyst is to obtain by ZSM-5 molecular sieve, aluminum oxide, tackiness agent being added water kneading, moulding, roasting.
9. method according to claim 8, the silica alumina ratio that it is characterized in that molecular sieve is 5～200, specific surface area is 200～500m
2/ g.
10. method according to claim 8, the roasting condition that it is characterized in that polymerizing catalyst is 400～600 ℃, the time is 2～8 hours.
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|---|---|---|---|
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Cited By (1)
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| CN114426453A (en) * | 2020-10-14 | 2022-05-03 | 中国石油化工股份有限公司 | Control method and system for three-section bed series connection pre-carbon-two hydrogenation reactor |
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| CN114426453A (en) * | 2020-10-14 | 2022-05-03 | 中国石油化工股份有限公司 | Control method and system for three-section bed series connection pre-carbon-two hydrogenation reactor |
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