CN1690028A - Catalytic distillation process for olefin production device - Google Patents
Catalytic distillation process for olefin production device Download PDFInfo
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- CN1690028A CN1690028A CNA2004100340372A CN200410034037A CN1690028A CN 1690028 A CN1690028 A CN 1690028A CN A2004100340372 A CNA2004100340372 A CN A2004100340372A CN 200410034037 A CN200410034037 A CN 200410034037A CN 1690028 A CN1690028 A CN 1690028A
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Abstract
The catalytic rectification method for olefin production includes setting catalytic reaction area in the pre-depropanizing column of the olefin producing apparatus; selectively hydrogenating C3- acetylene hydrocarbons and diene while separating C3, C3-, C4 and C4+ fractions; making top gaseous matter flow into gaseous hydrogenating reactor for further eliminating C3- acetylene hydrocarbons and diene; and feeding the cauldron liquid C4+ to the further separation area. The said method of the present invention can convert most of the C3- acetylene hydrocarbons and diene into corresponding olefin, reduce the hydrogen amount into the deeply freezing system, lower the power consumption, simplify technological process, reduce investment, raise the selectivity of catalytic hydrogenation and raise olefin yield, and has prolonged catalyst operating period, stable operation and no loss of butadiene.
Description
Technical field
The present invention relates to a kind of method that is used for olefin production plant, specifically, relate to a kind of method that is used for olefin production predepropanization front-end hydrogenation flow process carbon two, carbon three high unsaturated hydrocarbons component catalyst rectifying selection hydrogenation.
Background technology
In the process of hydrocarbon cracking system alkene, when generating ethene, propylene, butylene, can produce a spot of alkynes and diolefine.These alkynes and diolefine particularly can reduce the activity of polymerizing catalyst in the olefin polymerization process at the alkene post-treatment, and make the deterioration in physical properties of polymkeric substance, so must be removed.Industrial common employing catalysis selective hydrogenation method and solvent absorption are removed alkynes and the diolefine in the splitting gas.Because select the hydrogenation method technical process simple, energy expenditure is less, does not have environmental pollution, and the research and development of highly effective hydrogenation catalyzer success, so the application of catalysis selective hydrogenation method is general day by day.
Catalysis selective hydrogenation adopts hydrogenation catalyst, under certain process conditions, alkynes, diene hydrogenation is generated corresponding alkene or alkane, thereby reaches the purpose of purification.Catalysis selective hydrogenation comprises splitting gas selection hydrogenation, front-end hydrogenation and back end hydrogenation in the ethylene unit.Splitting gas without rectifying separation, just carries out the process of hydrogenation and removing alkynes after selecting hydrogenation to be meant that splitting gas removes sour gas such as carbonic acid gas, hydrogen sulfide through alkali cleaning.Owing to remove in five sections cracking gas compressor outlet logistics commonly used and contain hydrogen, methane, C
2Fraction and C
3Outside the fraction, also contain C based on divinyl
4Fraction and a small amount of C
5Diolefin, because the polymkeric substance that diene polymerization generates makes catalyst deactivation very fast, most of divinyl loses because of hydrogenation simultaneously when catalysis selective hydrogenation, so splitting gas selects the hydrogenation technique technology seldom to use industrial.
Front-end hydrogenation and back end hydrogenation technology are meant alkyne hydrogenation reactor for the position of demethanizing tower, and hydrogenator is front-end hydrogenation technology before being positioned at demethanizing tower, and hydrogenator is a back end hydrogenation technology after being positioned at demethanizing tower.Back end hydrogenation technology is separated carbon two fractions and the c 3 fraction obtain to splitting gas and is carried out catalysis selective hydrogenation respectively, and the acetylene in carbon two fractions, propine and propadiene in the c 3 fraction are removed.The used hydrogen of back end hydrogenation can be allocated into as required, improved hydrogenation selectivity, reduced the loss of purpose product, the hydrogenated products steady quality, but its weak point is that the flow process of separation system is comparatively complicated, for obtaining the high-purity ethylene product, second demethanizing tower need be set or adopt ethylene rectification tower side line discharging technology.
Splitting gas in the front-end hydrogenation technology without rectifying separation, just carries out acetylene hydrogenation after alkali cleaning.Front-end hydrogenation technology is divided front-end deethanization front-end hydrogenation and two kinds of technologies of predepropanization front-end hydrogenation.Front-end deethanization front-end hydrogenation technology is that front-end deethanization cat head material (methane, hydrogen, carbon monoxide and carbon two fractions) was passed through to select hydrogenation and removing acetylene wherein before entering demethanizing tower.Predepropanization front-end hydrogenation technology be with predepropanization cat head material (methane, hydrogen, carbon monoxide, carbon two fractions and c 3 fraction) before entering demethanizing tower by selecting hydrogenation and removing wherein acetylene and part propine, propadiene.Adopt front-end hydrogenation to remove alkynes technology, can simplify separation process, cryogenic energy utilization is reasonable, and the used hydrogen of hydrogenation reaction does not need outside the supply, only need select a kind of suitable hydrogenation catalyzer for use, can obtain polymer grade ethylene.In recent years since successfully develop have the ethylene selectivity height, the palladium catalyst that contains promotor of characteristics such as green oil generating amount is little, big air speed, make front-end hydrogenation remove the alkynes technology and adopted by increasing ethylene unit.But the shortcoming of front-end hydrogenation technology is to contain a large amount of hydrogen in the material, if catalyst selectivity is relatively poor, then side reaction acutely takes place, and not only causes ethene, propylene hydrogenation and suffers a loss, but also may cause temperature of reaction out of control, and even beds " temperature runaway " appears.In addition, when carbon monoxide content in the material fluctuates, also may cause reactor outlet leakage alkynes or operate abnormal phenomenon.
US 5,414,170 have proposed a kind of mixed phase foreshot acetylene hydrogenation technology, a kind of mixed phase hydrogenator of this process using, this reactor is positioned at the downstream side of predepropanization tower and the upstream side of further separating device such as demethanizing tower and deethanizing column, thereby the acetylene in the olefin production plant process-stream is carried out selective hydrogenation.For mixed phase acetylene hydrogenation reaction, the predepropanization tower that is positioned at its upstream provide liquid can for the mixed phase hydrogenator, makes its cleaning or cooling, can allow departing from and the abnormality of depropanizing tower of carbon monoxide and concentration of acetylene better.But the mixed phase hydrogenator in this technology can not make the complete hydrogenation of acetylene in the material, the gas phase hydrogenation reaction device also need be set further removing acetylene, and this technology is not handled to propine and propadiene.
CN1330131 provides a kind of method of carbon two～carbon ten high unsaturated hydrocarbons being carried out selective hydrogenation at the upstream side of olefin production plant predepropanization tower or front-end deethanization tower.After entering the mixed phase hydrogenator and carry out hydrogenation from the logistics of olefin hydrocarbon apparatus, enter predepropanization tower or front-end deethanization tower again.This method can be carried out selective hydrogenation to carbon two～carbon ten high unsaturated hydrocarbons that comprise acetylene, can reduce the reaction unit number of the complete hydrogenation of alkynes, can reduce the hydrogen content that enters predepropanization tower or front-end deethanization tower, deep cooling part, cut down the consumption of energy, can also reduce the diolefin content that enters predepropanization tower or front-end deethanization tower, reduce the coking of tower still.But this method diolefin that the industrial values such as divinyl in the charging is higher has also carried out hydrogenation, loses bigger.
At present, adopting maximum catalysis selective hydrogenation technology both at home and abroad is in Fixed Bed Gas Phase or liquid-phase hydrogenatin technology, for avoiding the beds temperature rise too high, generally will dilute raw material with the partial hydrogenation product in the production, the chance that this can increase the alkene deep hydrogenation is unfavorable for improving olefin yields.In addition, owing to alkynes, diolefine are easy to polymerization on catalyzer, the polymkeric substance of generation covers on the catalyst surface, because of can not in time thoroughly removing activity of such catalysts is reduced, and catalyzer needs repeated regeneration.
WO94/04477 discloses diolefine and alkynes catalytic distillation selection hydrogenation technique in a kind of carbon three logistics.This technology is combined in the catalysis selective hydrogenation with c 3 fraction of separating of carbon three and c4 fraction in the equipment and carries out, saved with fixed bed and selected the relevant major part investment of hydrogenation unit, make catalytic rectification process compare with the fixed-bed process of routine, investment significantly reduces; Constant voltage boiling system can guarantee that the temperature in catalytic distillation district accurately controls, and lower temperature of reaction and isothermal condition have improved the selectivity of hydrogenation, have reduced the generation of green oil; And the washing action of liquid-phase reflux significantly reduced the absorption of oligopolymer at catalyst surface, makes it to discharge from the tower still with heavy constituent, prolonged catalyst life.But this technology is a kind of back end hydrogenation flow process, and the required hydrogen of hydrogenation reaction need be allocated in addition.The type of feed of this process catalyst is a kind of harness formula structure, and its shortcoming is catalytic distillation element structure complexity, and catalyst distribution is inhomogeneous, utilization ratio is not high, and the bed partial drop of pressure is excessive, and the Liquid Flow situation is bad, liquid distribution is inhomogeneous, has influenced reaction efficiency.
CN1087334 has proposed a kind of steam cracking c 3 fraction catalytic distillation and has selected method of hydrotreating, the used selection hydrogenation catalyst of catalytic distillation tower is directly in bulk in beds in this method, have freeboard between granules of catalyst inside and the particle, the freeboard in the beds accounts for the 35-80% of beds volume.Catalyzer has catalysis and fractionated difunctional, and conversion zone does not need special internals, the filling of catalyzer and drawing off easily, and device structure is simple, the effective rate of utilization height.But because this method catalyzer has been made the random packing with refinery distillation, reaction efficiency must be affected, and random packing is difficult to satisfy the requirement of industrial high vapour-liquid load.In addition, large granular catalyst also exists problems such as being easy to fragmentation, the industrial difficulty greatly that implemented.
US 5,6792, and 41 have proposed a kind of preceding depentanize front-end hydrogenation catalytic rectification process.Splitting gas after three sections compressions, alkali cleaning, drying, at preceding depentanizer the C in the splitting gas
5 -And C
6 +Separate.This tower adopts catalytic rectification process, at rectifying section several catalyzed reaction beds, C in the splitting gas is set
2-C
5Alkynes in the fraction, diolefin hydrogenate are converted into corresponding alkene.By rectifying, be lighter than C
5Component separate from cat head, overweight C
6Component discharge from the tower still.Adopt this flow process, the hydrogen of 35%-45% reacts away in preceding depentanize catalytic rectifying tower in the splitting gas, and the hydrogen that therefore enters cryogenic system significantly reduces, and can reduce freezing energy consumption 7000KW, saves 40 equipment, reduces investment greatly.But this technology diolefin that the industrial values such as divinyl in the charging is higher has also carried out hydrogenation, loses bigger.In addition, the type of feed of this process catalyst has adopted CDTECH harness formula structure, and catalyst distribution is inhomogeneous, and utilization ratio is not high, and the bed partial drop of pressure is excessive, and the Liquid Flow situation is bad, and liquid distribution is inhomogeneous, has influenced reaction efficiency.
Summary of the invention
The object of the present invention is to provide a kind of being used for that the olefin production plant foreshot is carried out the method that catalytic distillation is selected hydrogenation, especially provide a kind of catalytic distillation that is used for predepropanization front-end hydrogenation flow process to select the method for hydrogenation.
Method of the present invention is provided with catalytic reaction zone by the depropanizing tower in olefin production plant, with the carbon in the splitting gas three and be lighter than c 3 fraction and (be called for short C
3 -) with carbon four and overweight c4 fraction and (be called for short C
4 +) carry out the isolating while, to C
3 -In alkynes and diolefine select hydrogenation.That is to say that method of the present invention is with traditional C
3 -And C
4 +Separation and C
3 -The selection hydrogenation of fraction combines, and carries out the isolation and selection hydrogenation reaction in a catalytic rectifying tower simultaneously.
The olefin production plant foreshot that is used for of the present invention carries out catalytic distillation to select the method for hydrogenation is that splitting gas is sent into depropanizing tower, with C
3 -With C
4 +Separate, at depropanizing tower some catalytic reaction zones are set, catalyzer is uniformly distributed in the catalytic reaction zone; Depropanizing cat head gaseous stream enters the gas phase hydrogenation reaction device, with C
3 -In alkynes and diolefine further remove; The depropanizing tower bottoms is C
4 +Fraction can directly be delivered to debutanizing tower.Particularly, comprise the following steps: successively
A) compressed, alkali cleaning, the dried raw material splitting gas from cracker enters depropanizing tower [1], and the lime set that produces in the splitting gas supercooler surge tank also enters depropanizing tower [1] after drying; In described depropanizing tower [1], catalytic reaction zone is set, in that being separated into, splitting gas is rich in carbon three C
3The gaseous stream C of light constituent more
3 -Be rich in carbon four C
4The liquid phase stream C of heavy constituent more
4 +The time, to vapor phase stream C
3 -In the major part of acetylene, propine and propadiene in catalytic reaction zone, optionally be hydrogenated to ethene and propylene respectively;
B) the gaseous stream C that obtains from depropanizing tower [1] cat head
3 -Enter gas phase hydrogenation reaction device [3] after compressed machine [2] compression, further remove C
3 -In alkynes and diolefine;
C) the liquid phase stream C that obtains from depropanizing tower [1] tower still
4 +Comprise carbon three C
3, carbon four and overweight the fraction of carbon four, deliver to further disengaging zone.
In the described depropanizing tower 1 continuously or at interval a plurality of catalytic reaction zones are set; Splitting gas divides sub-thread or multiply to enter corresponding catalytic reaction zone.
For the technical process of double tower predepropanization, method of the present invention is that catalytic reaction zone is arranged on high pressure depropanizer, C in high pressure depropanizer
3 -With C
4 +Separate C
3 -In the major part of acetylene, propine and propadiene in catalytic reaction zone, optionally be hydrogenated to ethene and propylene respectively.Concrete, predepropanization front-end hydrogenation catalytic rectification method of the present invention comprises the following steps: successively
A) compressed, alkali cleaning, the dried raw material splitting gas from cracker enters high pressure depropanizer 1, and the lime set that produces in the splitting gas supercooler surge tank also enters high pressure depropanizer 1 after drying; In described high pressure depropanizer 1, catalytic reaction zone is set, in that being separated into, splitting gas is rich in carbon three C
3The gaseous stream C of light constituent more
3 -With carbon containing three C
3, carbon four C
4The liquid phase stream C of heavy constituent more
4 +The time, to vapor phase stream C
3 -In alkynes and selected ethene and the propylene of being hydrogenated to of diolefine; General control high pressure depropanizer 1 tower top pressure is 1.2-2.0MPa, and the temperature of catalytic reaction zone is 0-50 ℃;
B) the gaseous stream C that obtains from high pressure depropanizer 1 cat head
3 -Enter gas phase hydrogenation reaction device 3 after compressed machine 2 compressions, further remove C
3 -In alkynes and diolefine; The pressure of preferred gas phase hydrogenation reaction device 3 is 3.0-4.0MPa, and temperature of reaction is 30-200 ℃;
C) liquid phase stream that obtains from high pressure depropanizer 1 tower still contains the c 3 fraction and the carbon four of a great deal of and overweights c4 fraction, delivers to low pressure depropanizing tower 4, further these fractions is separated; Cat head gas phase production material package is drawn together propane, propylene, propine and propadiene at interior cut; Tower bottoms phase production material package is drawn together carbon four and is overweighted the fraction of carbon four; The pressure of general control low pressure depropanizing tower 4 is 0.5-1.0Mpa;
D) deliver to further disengaging zone from the material of low pressure depropanizing tower 4 cats head, the extraction of tower still.
Carbon three in the described splitting gas and be lighter than c 3 fraction C
3 -Comprise methane, hydrogen, carbon monoxide, ethene, ethane, acetylene, propylene, propane, propine, propadiene; Carbon four and overweight c4 fraction C
4 +Comprise butylene, butane, butine, divinyl, C
5, C
6, benzene, toluene and other heavy fraction.
In the described high pressure depropanizer 1 continuously or at interval a plurality of catalytic reaction zones are set; Splitting gas divides sub-thread or multiply to enter corresponding catalytic reaction zone.
Preferred steps d) the cat head production described in all returns high pressure depropanizer 1 after condensation, the material of tower still extraction is delivered to debutanizing tower.
Preferred steps d) the cat head extraction material described in is after condensation, and the material of 30-60% (weight) returns high pressure depropanizer 1, and leftover materials are delivered to the propylene refining unit, and the material of tower still extraction is delivered to debutanizing tower.
In the step a), described selection hydrogenation catalyst is evenly distributed in the catalytic reaction zone of described high pressure depropanizer 1.The type of feed of preferred catalyst can adopt following one of several:
(1) granules of catalyst and structured packing built-up type
Described structured packing is the inertia ordered structure formula filler that can be used for rectifying separation, preferred stainless steel calendering corrugated plate regular packing, and its specification and size and catalytic rectifying tower adapt.
(a) during granules of catalyst was packed the silk screen container into, the silk screen container placed in the structured packing
Described silk screen container is formed by wire or nonmetal wire braiding, preferred stainless steel mesh is made, its pattern can be cylinder shape, oval column type, rhizoma sparganic column type, polygon prism type, pentagram prismatic, cross prismatic, type prismatic, character cut in bas-relief prismatic etc., and the structured packing of concrete specification and size and filling adapts.Preferred silk screen container places in the corrugated plate regular packing trough, each trough can be put one or more silk screen containers, perhaps, the silk screen container that catalyzer is housed is placed in each trough of structured packing at interval, but should be guaranteed catalyzer uniform distribution in whole cross section according to the loadings needs.In order to guarantee that member has good gas-liquid channel, the volume filling branch rate of preferred catalyst is 5-50%.
(b) granules of catalyst directly is assembled in structured packing
Granules of catalyst is without the silk screen container pack, but the waved plate of direct and structured packing is combined, and is uniformly distributed in the structured packing.
(2) granules of catalyst and column plate built-up type
Be deposited on the column plate behind the granules of catalyst organizine network capacity device parcel, the pattern of silk screen container can be ball-type, ring-like, cylinder shape, oval column type, rhizoma sparganic column type, polygon prism type, pentagram prismatic, cross prismatic, type prismatic, character cut in bas-relief prismatic etc., and the column plate of concrete specification and size and filling adapts; Or granules of catalyst directly is deposited on the column plate, catalyzer is fluidized state on column plate; Or with granules of catalyst be put on the column plate after the inertia filled media is mixed.
(3) catalyzer is directly made diffusing heap or the structured packing with centrifugation, is put in and promptly plays reaction and separation of double effect in the catalytic rectifying tower.
(4) other any type of feed that makes catalyzer be uniformly distributed in catalytic reaction zone.
Preferred described granules of catalyst can be solid sphere type, porous ball-type, filled circles column type, porous circular cylinder type, trifolium-shaped, multiaspect build, crossed cylinder type etc., the catalyst particle size size is decided with the granules of catalyst configuration of specifically selecting for use, and preferred diameter phi is the particle size of 1mm-6mm.
In the gentle phase hydrogenator of the catalytic reaction zone that any selective hydrogenation catalyst of knowing all can be used on high pressure depropanizer 1 of the present invention.Group VIII metal hydrogenation catalyzer the most generally uses, and is catalyzer preferably at present.
Preferred described selection hydrogenation catalyst is that in palladium, ruthenium, platinum, the nickel arsenide one or more are carried on the carrier, and carrier is selected from titanium dioxide, silicon oxide, aluminum oxide, zinc oxide, stannic oxide, molecular sieve or their mixture.
These catalyzer can also contain promotor, and promotor can be potassium, sodium, lithium, calcium, magnesium, barium, copper, silver, gold, zinc, lanthanum, cerium, molybdenum, tungsten, antimony, arsenic, bismuth, vanadium or their mixture.
In an embodiment preferred of the present invention, comprise the following steps: successively
A) in high pressure depropanizer 1, continuously or at interval a plurality of catalytic reaction zones are set, compressed, alkali cleaning, dried raw material splitting gas from cracker divide sub-thread or multiply to enter corresponding catalytic reaction zone in the high pressure depropanizer 1, and the lime set that produces in the splitting gas supercooler surge tank also enters high pressure depropanizer 1 after drying; In that being separated into, splitting gas is rich in carbon three C
3The gaseous stream C of light constituent more
3 -With carbon containing three C
3, carbon four C
4The liquid phase stream C of heavy constituent more
4 +The time, make vapor phase stream C
3 -In acetylene, propine and propadiene select to be hydrogenated to ethene and propylene; Wherein the uniform distribution active ingredient is selected from the selection hydrogenation catalyst of group VIII metal in catalytic reaction zone, and described granules of catalyst is packed in the silk screen container, and the silk screen container places in the structured packing or is deposited on the column plate;
B) the gaseous stream C that obtains from high pressure depropanizer 1 cat head
3 -Enter gas phase hydrogenation reaction device 3 after compressed machine 2 compressions, in the presence of the selection hydrogenation catalyst of group VIII metal, react, further remove C
3 -In acetylene, propine and propadiene;
C) liquid phase stream that obtains from high pressure depropanizer 1 tower still is delivered to low pressure depropanizing tower 4, further carbon three, carbon four and the fraction that overweights carbon four is separated; Cat head gas phase production material package is drawn together propane, propylene, propine and propadiene; Tower bottoms phase production material package is drawn together carbon four and is overweighted the fraction of carbon four;
D) deliver to the propylene refining tower from the material of low pressure depropanizing tower 4 cat head extraction, the material of tower still extraction is delivered to debutanizing tower.
According to the present invention, the hydroprocessing condition that adopts in depropanizing tower or gas phase hydrogenation reaction device can suitably change according to the composition and property of processed logistics.Normally, temperature and pressure will be enough to finish the hydrogenation of high unsaturated hydrocarbons contained in the logistics that is fed to hydrogenator, thereby can gain enlightenment according to above detailed description for the person skilled in the art the present invention is made various changes.For example, can adopt any known hydrogenation catalyst.
Method of the present invention is applied to existing predepropanization front-end hydrogenation flow process with catalytic rectification process, finishes C simultaneously in an equipment
3 -And C
4 +Separation and C
3 -The selection hydrogenation of fraction has the various advantages that catalytic distillation is selected hydrogenation, and is specific as follows described:
(1) because propine in the c 3 fraction and propadiene major part obtain conversion in high pressure depropanizer, small portion also can be removed by rectifying in the propylene refining tower, so can save the carbon three hydrogenator unit in the predepropanization process common process, simplified technology, reduced investment.
(2) because high pressure depropanizer is a catalytic rectifying tower, and the most of selective hydrogenation in catalytic rectifying tower of alkynes in carbon two, the c 3 fraction and diolefine is converted into corresponding alkene, makes the load of gas phase hydrogenation reaction device greatly reduce, equipment size reduces; Reduce the amounts of hydrogen that enters cryogenic system simultaneously, reduced energy consumption.
(3) in catalytic rectifying tower under vapour-liquid two phase separations, alkynes and diolefine are behind selected hydrogenation in the catalyst active center, be easy to desorption and leave the active centre, reduced the chance of deep hydrogenation, improved the selectivity and the olefin yields of catalysis selective hydrogenation.
(4) under centrifugation, can speed away beds and enter stripping section in dipolymer that forms on the catalyzer or polymer, the operational cycle of catalyzer is prolonged greatly.
(5) because temperature of reaction is strict controlled in the boiling point of material under the reaction pressure, reaction heat can only make more material vaporization, and bed can temperature runaway, helps improving olefin yields.
(6) because divinyl does not enter catalytic reaction zone, so in selecting hydrogenation, do not lose divinyl.
Method of the present invention has been simplified technology, has reduced energy consumption, has reduced investment, has improved the selectivity of catalysis selective hydrogenation, has increased olefin yields, has prolonged the operational cycle of catalyzer, and does not lose divinyl in selecting hydrogenation.
Description of drawings
Fig. 1 has described the schematic flow sheet of method of the present invention.
Fig. 2, Fig. 3, Fig. 4 have described the double-column process synoptic diagram of the preferred embodiment of method of the present invention.
1 depropanizing tower, 1 represents high pressure depropanizer in double-column process
2 compressors, 3 gas phase hydrogenation reaction devices, 4 low pressure depropanizing towers
Embodiment
Following example will give further instruction to the present invention, but not thereby limiting the invention.
Schematic flow sheet is referring to Fig. 2.
Catalytic reaction zone is arranged on about the high pressure depropanizer 1 splitting gas a feed entrance point, i.e. the 13rd, 14,15 plates.Catalyzer is φ 3-4mm ball-type hydrogenation catalyst BC-L-2000 (being produced by Sinopec Beijing Research Institute of Chemical Industry), catalyst loading pattern adopts granules of catalyst and structured packing built-up type, promptly select 125Y type stainless steel plate corrugated regular filler for use, dress φ 14mm stainless steel mesh cylinder in the trough, the granules of catalyst of packing in the cylinder, the volume fraction of catalyst loading is 20-25%.
Under these conditions, the transformation efficiency of acetylene is 80% in the high pressure depropanizer catalytic reaction zone, and the transformation efficiency of propine and propadiene is 85%, and the selectivity of alkynes and diolefine is all more than 90%.The cat head amounts of hydrogen can reduce 5.5% after increasing catalytic reaction zone.
If carbon three hydrogenators are not established in the propylene refining unit, then propine and propadiene (being called for short MAPD) directly enter the propylene refining tower, and extraction in tower bottoms, and MAPD concentration is 9.8 (mol) % in the still liquid.
Embodiment 2
Process flow diagram is referring to Fig. 3.
Catalytic reaction zone is arranged on about the high pressure depropanizer 1 splitting gas a feed entrance point, i.e. the 13rd, 14,15 plates.Catalyzer is φ 3-4mm ball-type hydrogenation catalyst BC-L-2000 (being produced by Sinopec Beijing Research Institute of Chemical Industry), in the ball-type silk screen container of earlier granules of catalyst being packed into during catalyst loading, and then is placed on the column plate.The volume fraction of catalyst loading is 20-25%.
Under these conditions, the transformation efficiency of acetylene is 80% in the high pressure depropanizer catalytic reaction zone, and the transformation efficiency of propine and propadiene is 94%, and the selectivity of alkynes and diolefine is all more than 90%.The cat head amounts of hydrogen can reduce 5.9% after increasing catalytic reaction zone.
Embodiment 3
Process flow diagram is referring to Fig. 3.
Catalytic reaction zone is arranged on about the high pressure depropanizer splitting gas feed entrance point, i.e. the 13rd, 14,15 plates.Catalyzer is φ 3-4mm ball-type hydrogenation catalyst BC-L-2000 (being produced by Sinopec Beijing Research Institute of Chemical Industry), earlier catalyzer is mixed with φ 4mm θ ring during catalyst loading, reinstall in the bar shaped silk screen container, and then be placed on the column plate.The volume fraction of catalyst loading is 20-25%.
Under these conditions, the transformation efficiency of acetylene is 80% in the high pressure depropanizer catalytic reaction zone, and the transformation efficiency of propine and propadiene is 88%, and the selectivity of alkynes and diolefine is all more than 90%.The cat head amounts of hydrogen can reduce 5.6% after increasing catalytic reaction zone.If do not establish carbon three hydrogenators, then propine and propadiene enter the propylene refining tower, extraction in tower bottoms, and MAPD concentration is 5.3 (mol) % in the still liquid.
Embodiment 4
Process flow diagram is referring to Fig. 4.
Catalytic reaction zone is provided with 2 altogether, respectively about high pressure depropanizer 1 splitting gas a feed entrance point, i.e. and the 13rd, 14,15 plates and the 19th, 20,21 plates.Catalyzer is φ 3-4mm ball-type BC-L-83A hydrogenation catalyst (being produced by Sinopec Beijing Research Institute of Chemical Industry), catalyst loading pattern adopts granules of catalyst and structured packing built-up type, promptly select 125Y shaped metal plate ripple arranged packing for use, dress φ 14mm stainless steel mesh cylinder in the trough, the granules of catalyst of packing in the cylinder, the volume fraction of catalyst loading is 20-25%.
Under these conditions, the transformation efficiency of acetylene is 80% in the high pressure depropanizer catalytic reaction zone, and the transformation efficiency of propine and propadiene is 94%, and the selectivity of alkynes and diolefine is all more than 90%.The cat head amounts of hydrogen can reduce 5.9% after increasing catalytic reaction zone.
Claims (22)
1, a kind of olefin production plant foreshot that is used for carries out the method that catalytic distillation is selected hydrogenation, it is characterized in that this method comprises the following steps: successively
A) compressed, alkali cleaning, the dried raw material splitting gas from cracker enters depropanizing tower [1], and the lime set that produces in the splitting gas supercooler surge tank also enters depropanizing tower [1] after drying; In described depropanizing tower [1], catalytic reaction zone is set, in that being separated into, splitting gas is rich in carbon three C
3The gaseous stream C of light constituent more
3 -Be rich in carbon four C
4The liquid phase stream C of heavy constituent more
4 +The time, to vapor phase stream C
3 -In alkynes and diolefine select hydrogenation;
B) the gaseous stream C that obtains from depropanizing tower [1] cat head
3 -Enter gas phase hydrogenation reaction device [3] after compressed machine [2] compression, further remove C
3 -In alkynes and diolefine;
C) the liquid phase stream C that obtains from depropanizing tower [1] tower still
4 +Comprise carbon three C
3, carbon four and overweight the fraction of carbon four, deliver to further disengaging zone.
2, method according to claim 1, it is characterized in that in described depropanizing tower [1] continuously or at interval a plurality of catalytic reaction zones are set; Splitting gas divides sub-thread or multiply to enter corresponding catalytic reaction zone.
3, method according to claim 1 is characterized in that the pressure of the gas phase hydrogenation reaction device [3] described in the step b) is 3.0-4.0MPa, and temperature of reaction is 30-200 ℃.
4, method according to claim 1 is characterized in that described depropanizing process is a double-column process, and wherein depropanizing tower [1] is a high pressure depropanizer, the liquid phase stream C that obtains from depropanizing tower [1] tower still
4 +Enter low pressure depropanizing tower [4] and further separate, comprise the following steps: successively
A) compressed, alkali cleaning, the dried raw material splitting gas from cracker enters high pressure depropanizer [1], and the lime set that produces in the splitting gas supercooler surge tank also enters high pressure depropanizer [1] after drying; In described high pressure depropanizer [1], catalytic reaction zone is set, in that being separated into, splitting gas is rich in carbon three C
3The gaseous stream C of light constituent more
3 -With carbon containing three C
3, carbon four C
4The liquid phase stream C of heavy constituent more
4 +The time, to vapor phase stream C
3 -In alkynes and diolefine select hydrogenation;
B) the gaseous stream C that obtains from high pressure depropanizer [1] cat head
3 -Enter gas phase hydrogenation reaction device [3] after compressed machine [2] compression, further remove C
3 -In alkynes and diolefine;
C) liquid phase stream that obtains from high pressure depropanizer [1] tower still is delivered to low pressure depropanizing tower [4], further carbon three, carbon four and the fraction that overweights carbon four is separated; Cat head gas phase production material package is drawn together propane, propylene, propine and propadiene at interior cut; Tower bottoms phase production material package is drawn together carbon four and is overweighted the fraction of carbon four;
D) deliver to further disengaging zone from the material of low pressure depropanizing tower [4] cat head, the extraction of tower still.
5, method according to claim 4 is characterized in that the high pressure depropanizer described in the step a) [1] tower top pressure is 1.2-2.0MPa, and the temperature of catalytic reaction zone is 0-50 ℃.
6, method according to claim 4 is characterized in that low pressure depropanizing tower [4] tower top pressure described in the step c) is 0.5-1.0Mpa.
7, method according to claim 4 is characterized in that the cat head production described in the step d) all returns high pressure depropanizer [1] after condensation, and the material of tower still extraction is delivered to debutanizing tower.
8, method according to claim 4, it is characterized in that the cat head extraction material described in the step d) is after condensation, the material of 30-60% (weight) returns high pressure depropanizer [1], and leftover materials are delivered to the propylene refining unit, and the material of tower still extraction is delivered to debutanizing tower.
9, method according to claim 4 is characterized in that in the step a), selects hydrogenation catalyst to be evenly distributed in the catalytic reaction zone of described high pressure depropanizer [1].
10, method according to claim 9, it is characterized in that described granules of catalyst can be selected from one of following manner in the filling of catalytic reaction zone: described granules of catalyst is uniformly distributed in the structured packing, and wherein said structured packing is the inertia ordered structure formula filler that can be used for rectifying separation; Described granules of catalyst is deposited on the column plate; Described granules of catalyst be put on the column plate after the inertia filled media is mixed.
11, method according to claim 10 is characterized in that described structured packing is a stainless steel calendering corrugated plate regular packing, and the waved plate of described granules of catalyst and structured packing is combined.
12, method according to claim 10 is characterized in that described granules of catalyst packs in the silk screen container, and the silk screen container places structured packing or is deposited on the column plate.
13, method according to claim 12 is characterized in that described silk screen container places in the corrugated plate regular packing trough, and each trough can be put one or more silk screen containers; Perhaps, guaranteeing that catalyzer under the equally distributed condition, will be equipped with silk screen container placement at interval in each trough of structured packing of catalyzer in whole cross section according to the loadings needs.
14, method according to claim 13, the volume fraction that it is characterized in that described catalyst loading is 5-50%.
15, method according to claim 12 is characterized in that described silk screen container is formed by wire or nonmetal wire braiding; Its pattern is ball-type, ring-like, cylinder shape, oval column type, rhizoma sparganic column type, polygon prism type, pentagram prismatic, cross prismatic, type prismatic or character cut in bas-relief prismatic.
16, method according to claim 15 is characterized in that described silk screen container made by stainless steel mesh.
17,, it is characterized in that the outer shape of described granules of catalyst is solid ball-type, porous ball-type, filled circles column type, porous circular cylinder type, trifolium-shaped, multiaspect build or crossed cylinder type according to the described method of one of claim 10-16.
18,, it is characterized in that described granules of catalyst diameter phi is 1mm-6mm according to the described method of one of claim 10-16.
19, method according to claim 4 is characterized in that the described catalyzer that is used for the gentle phase hydrogenator of high pressure depropanizer [1] catalytic reaction zone is the selection hydrogenation catalyst that active ingredient is selected from the group VIII metal.
20, method according to claim 19, it is characterized in that described catalyzer is with one or more are carried on the carrier in palladium, ruthenium, platinum and the nickel arsenide, described carrier is titanium dioxide, silicon oxide, aluminum oxide, zinc oxide, stannic oxide, molecular sieve or their mixture.
21, method according to claim 20 is characterized in that described catalyzer also contains the promotor that is selected from potassium, sodium, lithium, calcium, magnesium, barium, copper, silver, gold, zinc, lanthanum, cerium, molybdenum, tungsten, antimony, arsenic, bismuth, vanadium or their mixture.
22, a kind of olefin production plant front-end volatiles that are used for carry out the method that catalytic distillation is selected hydrogenation, it is characterized in that this method comprises the following steps: successively
A) in high pressure depropanizer [1], continuously or at interval a plurality of catalytic reaction zones are set, compressed, alkali cleaning, dried raw material splitting gas from cracker divide sub-thread or multiply to enter corresponding catalytic reaction zone in the high pressure depropanizer [1], and the lime set that produces in the splitting gas supercooler surge tank also enters high pressure depropanizer [1] after drying; In that being separated into, splitting gas is rich in carbon three C
3The gaseous stream C of light constituent more
3 -With carbon containing three C
3, carbon four C
4The liquid phase stream C of heavy constituent more
4 +The time, make vapor phase stream C
3 -In acetylene, propine and propadiene select to be hydrogenated to ethene and propylene; Wherein the uniform distribution active ingredient is selected from the selection hydrogenation catalyst of group VIII metal in catalytic reaction zone, and described granules of catalyst is packed in the silk screen container, and the silk screen container places in the structured packing or is deposited on the column plate;
B) the gaseous stream C that obtains from high pressure depropanizer [1] cat head
3 -Enter gas phase hydrogenation reaction device [3] after compressed machine [2] compression, in the presence of the selection hydrogenation catalyst of group VIII metal, react, further remove C
3 -In acetylene, propine and propadiene;
C) liquid phase stream that obtains from high pressure depropanizer [1] tower still is delivered to low pressure depropanizing tower [4], further carbon three, carbon four and the fraction that overweights carbon four is separated; Cat head gas phase production material package is drawn together propane, propylene, propine and propadiene; Tower bottoms phase production material package is drawn together carbon four and is overweighted the fraction of carbon four;
D) deliver to the propylene refining tower from the material of low pressure depropanizing tower [4] cat head extraction, the material of tower still extraction is delivered to debutanizing tower.
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| CNB2004100340372A CN1274649C (en) | 2004-04-22 | 2004-04-22 | Catalytic distillation process for olefin production device |
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| CNB2004100340372A CN1274649C (en) | 2004-04-22 | 2004-04-22 | Catalytic distillation process for olefin production device |
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| CN1274649C CN1274649C (en) | 2006-09-13 |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101844959A (en) * | 2009-03-26 | 2010-09-29 | 中国石油化工股份有限公司 | Cracked gas compression interstage selective hydrogenation method |
| CN102050690A (en) * | 2009-10-30 | 2011-05-11 | 中国石油化工股份有限公司 | Isoolefine production method |
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- 2004-04-22 CN CNB2004100340372A patent/CN1274649C/en not_active Expired - Lifetime
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| CN101423452B (en) * | 2007-10-31 | 2012-07-18 | 中国石油化工股份有限公司 | Selective hydrogenation method for fore-fraction high unsaturated hydrocarbons mixed phase |
| CN101450884B (en) * | 2007-12-07 | 2012-10-24 | 中国石油化工股份有限公司 | High unsaturated hydrocarbon selective hydrogenation method in cracking gas |
| CN101844959A (en) * | 2009-03-26 | 2010-09-29 | 中国石油化工股份有限公司 | Cracked gas compression interstage selective hydrogenation method |
| CN101844959B (en) * | 2009-03-26 | 2013-02-06 | 中国石油化工股份有限公司 | Method for selective hydrogenation between cracked gas compression sections |
| CN102050690A (en) * | 2009-10-30 | 2011-05-11 | 中国石油化工股份有限公司 | Isoolefine production method |
| CN102050690B (en) * | 2009-10-30 | 2014-04-02 | 中国石油化工股份有限公司 | Isoolefine production method |
| CN102464546A (en) * | 2011-08-17 | 2012-05-23 | 中国寰球工程公司 | Double-tower depropanization process for reducing reboiler scaling |
| CN103012033A (en) * | 2011-09-22 | 2013-04-03 | 西安石油大学 | Method for separating propylene and propane from liquid hydrocarbon |
| CN113721683A (en) * | 2020-05-25 | 2021-11-30 | 中国石油化工股份有限公司 | Automatic control method and equipment for carbon-three-liquid phase hydrogenation reactor |
| CN113721683B (en) * | 2020-05-25 | 2022-08-19 | 中国石油化工股份有限公司 | Automatic control method and equipment for carbon-three-liquid phase hydrogenation reactor |
| CN115029158A (en) * | 2022-06-14 | 2022-09-09 | 中海油天津化工研究设计院有限公司 | Refining method for liquefied petroleum gas hydrogen deep desulfurization and diene reduction |
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