CN101613621B - Method for selective hydrogenation and separation for pyrolysis gas - Google Patents
Method for selective hydrogenation and separation for pyrolysis gas Download PDFInfo
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Abstract
The invention discloses a method for selective hydrogenation and separation for pyrolysis gas, and belongs to the technical field of selective hydrogenation of unsaturated hydrocarbon. In order to solve the problems existing in the prior art that the liquid flow of a mixed phase hydrogenation reactor contains a large number of C3 and C4 components, cannot fully play a role in flushing in the reactor and repeatedly enters a front-end deethanization tower to cause high energy consumption, large equipment size, high operation cost and disadvantage to improve C3 selectivity and the like, the invention provides the method for selective hydrogenation for C2-C10 high unsaturated hydrocarbon (alkyne and diolefin) by using material flow at the bottom of the deethanization tower as liquid flow at the upstream side of the front-end deethanization tower of an olefin production device. The method enables the liquid flow of the mixed phase hydrogenation reactor to fully come into play, reduces the charging amount entering the front-end deethanization tower and energy consumption and equipment investment, and is favorable for improving the selectivity.
Description
Technical field
The present invention relates to a kind of alkynes and diolefin hydrogenate method, more particularly, the present invention relates to a kind of selection method of hydrotreating from alkynes and diolefine in the splitting gas of olefin production plant.
Background technology
Unless specialize, high unsaturated hydrocarbons of the present invention refers to contain the hydrocarbon of triple bond or two two keys.
At high temperature make the technique of the hydrocarbon conversion, for example steam heat cracking or catalytic pyrolysis can provide unsaturated hydrocarbons, for example ethene, acetylene, propylene, divinyl, butylene; Saturated alkane is such as ethane, propane, butane; Also just like the light component of methane, hydrogen and carbon monoxide and the boiling point hydro carbons in gasoline-range.The hydro carbons that in the gas phase monoolefine with two above carbon atoms that is obtained by these techniques, also contains a certain amount of higher degree of unsaturation, i.e. alkynes and diolefine.Generally speaking, in main logistics, contain 0.5%～5.3% alkynes and diolefine take alkene through what this method obtained.Alkynes and diolefine can reduce the activity of polymerizing catalyst, and make the deterioration in physical properties of polymkeric substance.So, the content of alkynes and diolefine is dropped to below the certain value, above-mentioned gas phase monoolefine could be as the monomer of synthetic polymer or multipolymer.
At present the most frequently used, economic and simple method is to make it to be converted into corresponding monoolefine by catalysis selective hydrogenation.Catalysis selective hydrogenation comprises selective hydrogenation of pyrolysis gas, " front-end hydrogenation " and " back end hydrogenation " three kinds of techniques.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 take divinyl as main C
4Fraction and a small amount of C
5Diolefin, the polymkeric substance that generates owing to diene polymerization when catalysis selective hydrogenation makes catalyst deactivation very fast, so the selective hydrogenation of pyrolysis gas Technology is seldom used in industry.
Described " front-end hydrogenation " and " back end hydrogenation " refer to alkyne hydrogenation reactor for the demethanizing tower position, and hydrogenator is front-end hydrogenation before being positioned at demethanizing tower, and hydrogenator is back end hydrogenation after being positioned at demethanizing tower.
Back end hydrogenation is to join quantitatively respectively in the deethanizing cat head material (carbon two fractions are only arranged) with demethanizing cat head material (methane, hydrogen and carbon monoxide) and by the material (methane and hydrogen) that methanator has been removed carbon monoxide and carbonic acid gas except alkynes, by selecting hydrogenation and removing alkynes wherein.Back end hydrogenation needs the outside liquid solvent, and because pressure is very sensitive for acetylene and carbon monoxide concentration offrating, the selectivity that the amount that needs careful control to add hydrogen and CO during therefore except acetylene is regulated carbon two hydrogenation catalysts.In addition and since the purity of ethylene product be subjected to hydrogen import impurity (such as CO, methane etc.) impact and the time have fluctuation, downstream ethylene column need establish " bar formula rectifying section ", or the second demethanizing tower is set to separate remaining hydrogen and methane.
Front-end hydrogenation just occurs except the alkynes technology fifties, in recent years, have the ethylene selectivity height owing to successfully develop, green oil generating amount is little, the palladium catalyst that contains promotor of the characteristics such as large air speed makes front-end hydrogenation remove the acetylene technology and is adopted by increasing ethylene unit.The front-end hydrogenation technology has front-end deethanization front-end hydrogenation and two kinds of techniques of predepropanization front-end hydrogenation.Front-end deethanization front-end hydrogenation technique 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 technique is with predepropanization cat head material (methane, hydrogen, carbon monoxide, C
2Fraction and C
3Fraction) before entering demethanizing tower by selecting hydrogenation and removing wherein acetylene and part propine, propadiene.The shortcoming of front-end hydrogenation technology is owing to contain a large amount of hydrogen and carbon monoxide content fluctuation in the material, cause reactor outlet to leak easily alkynes or operate abnormal phenomenon, these abnormalities are owing to go into operation susceptibility and the active temperature excursion that causes of initial stage live catalyst of ethylene unit produces.In addition, hydrogen is to separate in the higher demethanizing tower system of energy consumption with methane, so it is higher to enter the hydrogen content of demethanizing tower, energy consumption is higher.
Chinese patent application CN1098709A (application on May 12nd, 94) discloses a kind of mixed phase front end C 2 acetylene hydrogenation technique.Introduce this patent application as a reference in full herein.A kind of mixed phase hydrogenator has been adopted in this patent application, and this reactor is positioned at downstream side and the further separating device of predepropanization tower, such as the upstream side of demethanizing tower and deethanizing column.The advantage of this patent is: for the reaction of mixed phase acetylene hydrogenation, the predepropanization tower that is located thereon trip can provide liquid to the mixed phase hydrogenator, makes its cleaning or cooling.Can also reduce the number of the front-end hydrogenation reaction unit that makes the alkynes complete hydrogenation, find that also this hydrogenation unit can allow departing from of carbon monoxide and concentration of acetylene better, and the abnormality of depropanizing tower.The shortcoming of this patent is: 1, because this patent application is placed on the downstream side of predepropanization tower with the mixed phase hydrogenator, that enter the mixed phase hydrogenator is the C that is rich in that has cooled off with partial condensation
3The logistics of lighter component, so this patented technology can only be carried out hydrogenation to low-carbon (LC) alkynes in the mixed phase hydrogenator, can not carry out hydrotreatment to high-carbon unsaturated hydrocarbons such as butine, divinyl, so the amounts of hydrogen that consumes is limited, a large amount of remaining hydrogens enter splitting gas deep cooling part, and energy consumption is higher.2, remaining high-carbon alkynes and diolefine can reduce the activity of polymerizing catalyst as entering polymerization process, and make the deterioration in physical properties of polymkeric substance.3, because this patent application is not carried out hydrotreatment to the logistics that enters the predepropanization tower, the alkynes in the logistics and diolefin cause the tower reactor coking easily, and can increase energy consumption.4, because when utilizing this patent application technology, also need add a series of equipment with to isolated C
3And C
3Above component removes respectively in addition alkynes and removes diolefin and process, thereby has increased on the whole facility investment and production energy consumption.
In order to solve the problems referred to above of CN1098709A, Chinese patent CN 1109090C has proposed the method for carbon two～carbon ten high unsaturated hydrocarbons (alkynes and diolefine) being carried out selective hydrogenation at predepropanization tower or front-end deethanization tower upstream side.Make cleavage product stream from alkene enter the mixed phase hydrogenator and select hydrogenation, then enter predepropanization tower or front-end deethanization tower, the liquid phase stream part of tower reactor loops back the mixed phase hydrogenator and washes beds as liquid phase stream.This patented technology can reduce the reaction unit number of alkynes complete hydrogenation, reduce the hydrogen content enter predepropanization tower or front-end deethanization tower, deep cooling part, reduce energy consumption and equipment size, also can reduce the diolefin content that enters predepropanization tower or front ethane tower, reduce the tower reactor coking amount and reduce energy consumption.But this patented technology also exists problem, for example, uses the liquid phase stream of predepropanization tower or the extraction of front ethane tower tower reactor as the liquid phase stream of mixed phase hydrogenator, and component is lighter in this part liquid phase stream.In the situation that adopts the predepropanization tower, the liquid phase stream that loops back the mixed phase hydrogenator contains a large amount of carbon four, carbon five components.In the situation of ethane tower, the liquid phase stream that loops back the mixed phase hydrogenator contains a large amount of carbon three, carbon four, carbon five components before employing.Carbon three components are gas phase in the mixed phase hydrogenator, carbon four components major part is gas phase, they can not play the flushing beds fully, they repeat to enter predepropanization tower or front ethane tower simultaneously, and this has increased energy consumption, equipment size and the running cost of predepropanization tower or front ethane tower undoubtedly.In the situation of ethane tower, the liquid phase stream that loops back the mixed phase hydrogenator contains propylene before employing, and this selectivity for the mixed phase hydrogenation is very unfavorable, causes propylene loss.
Therefore, need a kind of method that high unsaturated hydrocarbons in the product stream of cracker can be carried out hydrogenation and can overcome the above-mentioned shortcoming of prior art.
Summary of the invention
The purpose of this invention is to provide a kind ofly for from the selective hydrogenation of pyrolysis gas of olefin production plant and the method for separating, the method can be selected hydrogenation and can overcome the above-mentioned shortcoming of prior art carbon two～carbon ten high unsaturated hydrocarbons that comprise acetylene in the splitting gas.
More particularly, the present invention thinks over the tower reactor extraction logistics that adopts a kind of mixed phase hydrogenator, this reactor to be positioned at front-end deethanization tower upstream side and adopt debutanizing tower as liquid phase stream.
Generally speaking, the invention provides a kind of for the treatment of containing hydrogen, carbon monoxide, methane, acetylene, ethene, ethane, propylene, propane, methylacetylene, propadiene, butylene, butane, butine, divinyl, C
5, C
6, benzene, toluene, C
8And C
9And C
10The method of the raw material of fraction mixture or their mixture, the method comprises the following steps:
(1) splitting gas from olefin hydrocarbon apparatus enters the mixed phase hydrogenator, make wherein alkynes and at least a portion of diolefin carry out the mixed phase hydrogenation reaction;
(2) will deliver to the front-end deethanization tower from the effluent of mixed phase hydrogenator, and be separated into and be rich in C
2And more light constituent vapor phase stream and be rich in C
3And the liquid phase stream of more recombinating and dividing;
(3) vapor phase stream that step (2) is obtained is delivered to carbon two front-end hydrogenation reactors and is carried out gas phase hydrogenation reaction; The liquid phase stream that step (2) obtains is delivered to depropanizing tower, be separated into and be rich in C
3Logistics and be rich in carbon four and the more logistics of restructuring minute, be rich in C
3Logistics deliver to the propylene refining unit;
(4) debutanizing tower is delivered in the logistics that is rich in carbon four and more restructuring minute that step (3) is obtained, the logistics that is separated into the logistics that is rich in C-4-fraction and comprises carbon five and more recombinate and divide, the logistics circulation that a part is comprised carbon five and more restructuring minute enters mixed phase hydrogenator, remainder extraction.
Described splitting gas from olefin hydrocarbon apparatus is preferably from the product stream of steam cracking device or cat-cracker.
Described splitting gas from olefin hydrocarbon apparatus preferably comprises hydrogen, methane, carbon monoxide, acetylene, ethene, ethane, propylene, propane, butylene, butine, 1,3-butadiene, butane, C
5Non-aromatics, C
6Non-aromatics, C
7Non-aromatics, C
8Non-aromatics, benzene, toluene, vinylbenzene or their mixture.
Preferred described mixed phase hydrogenation reaction and operates in the presence of the mixed phase hydrogenation catalyst that includes group VIII metal or I subgroup metal under 10 ℃～100 ℃ temperature and 0.7MPa～4.0MPa pressure condition.
Preferred described mixed phase hydrogenation catalyst is that in palladium, ruthenium, platinum, the nickel arsenide one or more are carried on the carrier, and described carrier is selected from titanium dioxide, silicon oxide, aluminum oxide, zinc oxide, stannic oxide, molecular sieve or their mixture.
Preferred described mixed phase hydrogenation catalyst 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.
Preferred described carbon two front-end hydrogenation reactors are at 30 ℃～200 ℃ temperature and 0.6MPa～4.0MPa pressure, operate containing in the presence of the group VIII metal hydrogenation catalyzer.
The described group VIII metal hydrogenation catalyzer that contains preferably is carried in palladium, ruthenium, platinum, the nickel arsenide one or more on carrier, and described carrier is selected from titanium dioxide, silicon oxide, aluminum oxide, zinc oxide, stannic oxide, molecular sieve or their mixture.
The preferred described group VIII metal hydrogenation catalyzer that contains 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.
The preferred selective hydrogenation of pyrolysis gas of the present invention and the method for separating may further comprise the steps:
The splitting gas that a. will contain alkene is by heat exchanger cooling to 10 ℃～100 ℃;
B. will send into the mixed phase hydrogenator from the material of step a, at least wherein part alkynes and diolefin be carried out selective hydrogenation;
C. will cool off through water cooler from the effluent of mixed phase hydrogenator, the front-end deethanization tower is sent in logistics after the cooling, is separated into and is rich in C
2And more light constituent gaseous stream and be rich in C
3And the liquid phase stream of more recombinating and dividing, said front-end deethanization tower operates under 2.0MPa～4.5MPa pressure;
D. with the described C that is rich in
2More the gaseous stream of light constituent is delivered to carbon two front-end hydrogenation reactors, and wherein contained acetylene is carried out selective hydrogenation;
E. with the described C that is rich in
3Reach the liquid phase stream of dividing of more recombinating and deliver to depropanizing tower, the logistics that is separated into the logistics that is rich in carbon three and is rich in carbon four and more recombinates and divide is delivered to the propylene refining unit with the logistics that is rich in carbon three;
F. debutanizing tower is delivered in the described logistics that is rich in carbon four and more restructuring minute, the logistics that is separated into the logistics that is rich in carbon four and comprises carbon five and more recombinate and divide, mixed phase hydrogenator, remainder extraction are sent in the logistics circulation that a part is comprised carbon five and more restructuring minute;
G. will cool off and partial condensation from the gaseous stream of carbon two front-end hydrogenation reactors, and the logistics of condensation is recycled to the top of front-end deethanization tower as phegma;
H. will deliver to the downstream separation district from the uncooled gaseous stream of carbon two front-end hydrogenation reactors.
Any suitable selective hydrogenation catalyst of knowing all can be used in mixed phase of the present invention or the carbon two front-end hydrogenation reactors.Group VIII metal hydrogenation catalyzer the most generally uses, and is present catalyzer preferably.Group VIII metal hydrogenation catalyzer the most generally uses, and is present catalyzer preferably.The group VIII metal loads on a kind of carrier, such as aluminum oxide usually.A kind of catalyzer of successful Application is the group VIII metal that has flooded about 0.1%～about 1% scope, and these and other catalyzer more specifically disclose in the literature.The disclosed example of these prior aries has: with regard to carrier, the catalyzer great majority that are used for alkynes and selective hydrogenation of diolefin as are the palladium catalysts take aluminum oxide as carrier, see US patent US-3679762 and US Patent No.-4762956; Also have with TiO
2Be the palladium catalyst of carrier, see US Patent No.-4839329; With SiO
2Be the palladium-zinc catalyst of carrier, see German patent application DE-A2156544; With CaCO
3Be the palladium of carrier-plumbous catalyzer; And be stated from palladium catalyst on the cordierite honeycomb carrier of alkali metal containing and/or alkaline-earth metal, see Chinese patent application CN-1176291A.With regard to the active ingredient of catalyzer, prior art also comprises the palladium catalyst that adds promotor, US Patent No. 4,404, and 124 disclosed promotors are silver; The disclosed promotor of European patent application EP-A892252 is gold; German patent application DE-A1284403 and US Patent No. 4,577,047 disclosed promotor are chromium; US Patent No. 3,912,789 disclosed promotors are copper; US Patent No. 3,900,526 disclosed promotors are iron; US Patent No. 3,489,809 disclosed promotors are rhodium; US Patent No. 3,325,556 disclosed promotors are lithium; The disclosed promotor of Chinese patent application CN 1151908A is potassium.In addition, US Patent No.-4571442; US Patent No.-4347392; US Patent No.-4128595; US Patent No.-5059732 and US Patent No.-5414170 also discloses catalyst component and the technique of alkynes and selective hydrogenation of diolefin as.
Above mentioned patent, patent application and publication all be introduced as in full reference of the present invention.
According to the present invention, the hydroprocessing condition that adopts in mixed phase or carbon two front-end hydrogenation reactors can suitably change according to the composition and property of processed logistics.Normally, temperature and pressure will be enough to finish the basically hydrogenation of all high unsaturated hydrocarbons contained in the logistics that is fed to carbon two front-end hydrogenation reactors, usually, it is to operate under 0.7MPa～4.0MPa with pressure range that hydrogenation technique is 10 ℃～90 ℃ in temperature range, in hydrogenation process, can adopt the contact method of fixed bed catalyst or other types well-known to those skilled in the art to carry out technological process.
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.And reactor can be fixed bed form or other forms useful to the alkynes hydrogenation technique.
And for example, in another embodiment of the invention, the top gaseous phase stream that can make the front-end deethanization tower directly carries out low pressure without compression, and (gas phase hydrogenation reaction of 0.6MPa～1.8MPa) can save compressor like this.
In the present invention, described mixed phase hydrogenation refers to have gas phase and two kinds of logistics of liquid phase at beds.
The liquid phase material of the present invention at the bottom of with front debutylize Tata (it consists of carbon five and more restructuring minute) turns back to the mixed phase hydrogenator, can provide liquid to clean and cooling performance, remove a large amount of reaction heat, reactor can be simulated a kind of isothermal reactor, improve selectivity and the security of hydrogenation, improve catalyst life.CN1109090C compares with Chinese patent, substantially do not contain carbon three, carbon four components in this liquid phase material, avoid carbon three, carbon four components in mixed phase hydrogenator and front-end deethanization tower, to circulate, so that this liquid phase material can play predictive role fully, simultaneously can reduce the inlet amount that enters the front-end deethanization tower, reduce energy consumption and equipment size and the running cost of front-end deethanization tower, be conducive to simultaneously improve the selectivity of carbon three hydrogenation.
The contriver finds by at front-end deethanization tower upstream side the mixed phase hydrogenator being set, and the mixed phase hydrogenator is introduced in the liquid phase stream circulation of debutanizing tower, the advantage that not only can clean or cool off the mixed phase hydrogenator can also be to comprising the C of acetylene
2～C
10High unsaturated hydrocarbons carries out selective hydrogenation, has greatly enlarged the hydrogenation scope.
In addition, the contriver unexpectedly finds can greatly reduce the coking amount of tower reactor because logistics has removed a large amount of high unsaturated hydrocarbons before entering the front-end deethanization tower, and reduces energy consumption.
The present invention can reduce the reaction unit number of alkynes complete hydrogenation, enters the hydrogen content of predepropanization tower, deep cooling part with minimizing, reduces energy consumption and equipment size.The present invention also can reduce the diolefin content that enters the front-end deethanization tower, reduces the tower reactor coking amount and reduces energy consumption.
Description of drawings
Fig. 1 is the synoptic diagram of the method for expression selective hydrogenation of pyrolysis gas of the present invention and separation.
Nomenclature:
1 mixed phase hydrogenator; 2 front-end deethanization towers; 3 depropanizing towers; 4 debutanizing towers; 5 carbon, two front-end hydrogenation reactors; 6 carbon, three hydrogenators.
Embodiment
Further explain selective hydrogenation of pyrolysis gas of the present invention and the method for separating below in conjunction with accompanying drawing.
Of the present invention for olefin production plant C
2～C
10High unsaturated hydrocarbons is selected the method for hydrogenation, may further comprise the steps:
(1) splitting gas from olefin hydrocarbon apparatus enters mixed phase hydrogenator 1, make wherein alkynes and at least a portion of diolefin carry out the mixed phase hydrogenation reaction;
(2) will deliver to front-end deethanization tower 2 from the effluent of mixed phase hydrogenator 1, and be separated into and be rich in C
2And more light constituent vapor phase stream and be rich in C
3And the liquid phase stream of more recombinating and dividing;
(3) vapor phase stream that step (2) is obtained is delivered to carbon two front-end hydrogenation reactors 5 and is carried out gas phase hydrogenation reaction; The liquid phase stream that step (2) obtains is delivered to depropanizing tower 3, be separated into and be rich in C
3Logistics and be rich in carbon four and the more logistics of restructuring minute, be rich in C
3Logistics deliver to carbon three hydrogenators 6;
(4) debutanizing tower 4 is delivered in the logistics that is rich in carbon four and more restructuring minute that step (3) is obtained, the logistics that is separated into the logistics that is rich in C-4-fraction and comprises carbon five and more recombinate and divide, the logistics circulation that a part is comprised carbon five and more restructuring minute enters mixed phase hydrogenator 1, remainder extraction.
Preferably, the selective hydrogenation of pyrolysis gas for olefin production plant of the present invention preferably includes following steps with the method for separating:
The splitting gas that a. will contain alkene is by heat exchanger cooling to 10 ℃～100 ℃;
B. will send into mixed phase hydrogenator 1 from the material of step a, at least wherein part high unsaturated hydrocarbons be carried out selective hydrogenation;
C. will cool off through water cooler from the effluent of mixed phase hydrogenator 1, front-end deethanization tower 2 is sent in logistics after the cooling, is separated into and is rich in C
2And more light constituent gaseous stream and be rich in C
3And the liquid phase stream of more recombinating and dividing, said front-end deethanization tower 2 operates under 2.0MPa～4.5MPa pressure;
D. with the described C that is rich in
2More the gaseous stream of light constituent is delivered to carbon two front-end hydrogenation reactors 5, and wherein contained acetylene is carried out selective hydrogenation,
E. with the described C that is rich in
3Reach the liquid phase stream of dividing of more recombinating and deliver to depropanizing tower 3, the logistics that is separated into the logistics that is rich in carbon three and is rich in carbon four and more recombinates and divide is delivered to carbon three hydrogenators 6 with the logistics that is rich in carbon three;
F. debutanizing tower 4 is delivered in the described logistics that is rich in carbon four and more restructuring minute, the logistics that is separated into the logistics that is rich in carbon four and comprises carbon five and more recombinate and divide, mixed phase hydrogenator 1, remainder extraction are sent in the logistics circulation that a part is comprised carbon five and more restructuring minute;
G. will cool off and partial condensation from the gaseous stream of carbon two front-end hydrogenation reactors 5, and the logistics of condensation is recycled to the top of front-end deethanization tower 2 as phegma;
H. will deliver to the downstream separation district from the uncooled gaseous stream of carbon two front-end hydrogenation reactors 5.
Referring to Fig. 1, the phase feed that contains alkene 1 that from steam cracking device, obtains, concrete composition can mix with the liquid phase stream of coming at the bottom of debutanizing tower with reference to table 1, then carries out heat exchange in heat exchanger, enters mixed phase hydrogenator 1.Mixed phase hydrogenator 1 is in relatively low temperature range (about 30 ℃～100 ℃) and relative medium pressure range (under about 1.0～3.0MPa), in the presence of BC-L-83A hydrogenation catalyst (Beijing Chemical Institute of China Petrochemical Corporation's production), operate so that most acetylene hydrogenation, for example remain the acetylene of 100ppm (mole), this is that propine and propadiene transformation efficiency are about 50%, and carbon four above diolefine transformation efficiencys are about 80%.From mixed phase hydrogenator reaction product out, cool off through supercooler, enter front-end deethanization tower 2, be separated into a kind of liquid phase stream and vapor phase stream, gaseous stream enters carbon two front-end hydrogenation reactors and acetylene hydrogenation is removed (catalyzer that uses is produced as the Beijing Chemical Institute of China Petrochemical Corporation), the temperature and pressure condition that adopts will be enough to and will enter all acetylene hydrogenations in the gas phase hydrogenation reaction device, in general, hydrogenation temperature is 30 ℃～200 ℃, and pressure is 1.0MPa～4.0MPa.From carbon two front-end hydrogenation reactors 5 effluent out through the heat exchanger partial condensation, gas-liquid separation in separating tank, liquid phase is delivered to the front-end deethanization column overhead as the backflow of front-end deethanization tower 2, gas phase enters the separating device of cooler downstream.Liquid phase stream from the front-end deethanization tower enters depropanizing tower 3.From depropanizing tower 3 isolated carbon three logistics, through heat exchanger heats, enter in carbon three hydrogenators 6 (catalyzer that uses is produced as the Beijing Chemical Institute of China Petrochemical Corporation).This area that operates in of depropanizing tower and carbon three hydrogenators is mature technology, repeats no more here.Logistics from the depropanizing tower reactor enters debutanizing tower, is separated into carbon four logistics and comprises carbon five to reach the logistics that more restructuring divides, and a part comprises carbon five and the logistics that divides of more recombinating turns back to mixed phase hydrogenator 1, the rest part extraction.
Because the concrete operations parameter is influenced each other by the control Index Influence of unit and pressure, temperature and flow etc., those skilled in the art can easily determine these parameters according to concrete practical situation in addition, therefore present embodiment does not provide the concrete operations parameter, and this does not affect the enforcement of present embodiment.Usually industrial also is to operate in a scope, rather than at a point operation, according to the hydrogenation result, operator can in time change operating parameters.
Table 1 raw material composition (% by mole)
| Component | Quality % | Component | Quality % |
| Hydrogen | 0.95 | Butane | 0.15 |
| Methane | 16.0 | Carbon five | 3.25 |
| Ethane | 3.85 | C 6-8Non-aromatics | 2.65 |
| Ethene | 28.1 | Benzene | 6.9 |
| Acetylene | 0.8 | Toluene | 3.1 |
| Propane | 0.25 | Dimethylbenzene | 1.6 |
| Propylene | 15.0 | Vinylbenzene | 1.05 |
| Propine, propadiene | 1.3 | Pyrolysis gasoline | 1.9 |
| 1,3-butadiene | 1.7 | Oil fuel | 4.3 |
| Butylene | 4.15 |
Claims (10)
1. method that is used for selective hydrogenation of pyrolysis gas and separation may further comprise the steps:
(1) splitting gas from olefin hydrocarbon apparatus enters the mixed phase hydrogenator, make wherein alkynes and at least a portion of diolefin carry out the mixed phase hydrogenation reaction;
(2) will deliver to the front-end deethanization tower from the effluent of mixed phase hydrogenator, and be separated into and be rich in C
2And more light constituent vapor phase stream and be rich in C
3And the liquid phase stream of more recombinating and dividing;
(3) vapor phase stream that step (2) is obtained is delivered to carbon two front-end hydrogenation reactors and is carried out gas phase hydrogenation reaction; The liquid phase stream that step (2) obtains is delivered to depropanizing tower, be separated into and be rich in C
3Logistics and be rich in carbon four and the more logistics of restructuring minute, be rich in C
3Logistics deliver to the propylene refining unit;
(4) debutanizing tower is delivered in the logistics that is rich in carbon four and more restructuring minute that step (3) is obtained, the logistics that is separated into the logistics that is rich in C-4-fraction and comprises carbon five and more recombinate and divide, the logistics circulation that a part is comprised carbon five and more restructuring minute enters mixed phase hydrogenator, remainder extraction.
2. the method for claim 1, wherein said splitting gas from olefin hydrocarbon apparatus is the product stream from steam cracking device or cat-cracker.
3. the method for claim 1, wherein said splitting gas from olefin hydrocarbon apparatus comprises hydrogen, methane, carbon monoxide, acetylene, ethene, ethane, propylene, propane, butylene, butine, 1,3-butadiene, butane, C
5Non-aromatics, C
6Non-aromatics, C
7Non-aromatics, C
8Non-aromatics, benzene, toluene, vinylbenzene or their mixture.
4. the method for claim 1, wherein said mixed phase hydrogenation reaction and operates in the presence of the mixed phase hydrogenation catalyst that includes group VIII metal or I subgroup metal under 10 ℃～100 ℃ temperature and 0.7MPa～4.0MPa pressure condition.
5. method as claimed in claim 4, wherein said mixed phase hydrogenation catalyst is that in palladium, ruthenium, platinum, the nickel arsenide one or more are carried on the carrier, and described carrier is selected from titanium dioxide, silicon oxide, aluminum oxide, zinc oxide, stannic oxide, molecular sieve or their mixture.
6. method as claimed in claim 5, wherein said mixed phase hydrogenation catalyst 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.
7. the method for claim 1, wherein said carbon two front-end hydrogenation reactors be at 30 ℃～200 ℃ temperature and 0.6MPa～4.0MPa pressure, operates containing in the presence of the group VIII metal hydrogenation catalyzer.
8. method as claimed in claim 7, the wherein said group VIII metal hydrogenation catalyzer that contains is that in palladium, ruthenium, platinum, the nickel arsenide one or more are carried on the carrier, and described carrier is selected from titanium dioxide, silicon oxide, aluminum oxide, zinc oxide, stannic oxide, molecular sieve or their mixture.
9. method as claimed in claim 8, the wherein said group VIII metal hydrogenation catalyzer that contains 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.
10. the method for claim 1 may further comprise the steps:
The splitting gas that a. will contain alkene is by heat exchanger cooling to 10 ℃～100 ℃;
B. will send into the mixed phase hydrogenator from the material of step a, at least wherein part alkynes and diolefin be carried out selective hydrogenation;
C. will cool off through water cooler from the effluent of mixed phase hydrogenator, the front-end deethanization tower is sent in logistics after the cooling, is separated into and is rich in C
2And more light constituent gaseous stream and be rich in C
3And the liquid phase stream of more recombinating and dividing, said front-end deethanization tower operates under 2.0MPa～4.5MPa pressure;
D. with the described C that is rich in
2More the gaseous stream of light constituent is delivered to carbon two front-end hydrogenation reactors, and wherein contained acetylene is carried out selective hydrogenation;
E. with the described C that is rich in
3Reach the liquid phase stream of dividing of more recombinating and deliver to depropanizing tower, the logistics that is separated into the logistics that is rich in carbon three and is rich in carbon four and more recombinates and divide is delivered to the propylene refining unit with the logistics that is rich in carbon three;
F. debutanizing tower is delivered in the described logistics that is rich in carbon four and more restructuring minute, the logistics that is separated into the logistics that is rich in carbon four and comprises carbon five and more recombinate and divide, mixed phase hydrogenator, remainder extraction are sent in the logistics circulation that a part is comprised carbon five and more restructuring minute;
G. will cool off and partial condensation from the gaseous stream of carbon two front-end hydrogenation reactors, and the logistics of condensation is recycled to the top of front-end deethanization tower as phegma;
H. will deliver to the downstream separation district from the uncooled gaseous stream of carbon two front-end hydrogenation reactors.
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| CN 200810115610 CN101613621B (en) | 2008-06-26 | 2008-06-26 | Method for selective hydrogenation and separation for pyrolysis gas |
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| CN102220168B (en) * | 2010-04-13 | 2014-01-08 | 中国石油化工股份有限公司 | Method for selective hydrogenation of pyrolysis gas |
| CN102234543A (en) * | 2010-04-20 | 2011-11-09 | 中国石油化工股份有限公司 | Method for prolonging service life of pyrolysis gas mixed phase hydrogenation catalyst |
| CN102408916B (en) * | 2010-09-21 | 2014-05-28 | 中国石油化工股份有限公司 | Method for removing alkine and dialkene from pyrolysis gas through selective hydrogenation |
| CN102924218B (en) * | 2012-11-09 | 2014-07-09 | 北京斯伯乐科学技术研究院 | Multifunctional antioxidant for benzene preparing device and using method thereof |
| CN105732280B (en) * | 2014-12-12 | 2017-12-19 | 中国石油天然气股份有限公司 | Hydrogenation method before deethanization of carbon-containing distillate |
| CN107970927B (en) * | 2016-10-24 | 2019-11-12 | 中国石油化工股份有限公司 | Selective hydrogenation of pyrolysis gas catalyst, preparation method and method of hydrotreating |
| CN114471375B (en) * | 2020-10-23 | 2023-02-24 | 中国石油化工股份有限公司 | Device and method for fully hydrogenating mixed C4 material flow |
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