CN101613621A - Splitting gas is selected hydrogenation and separation method - Google Patents
Splitting gas is selected hydrogenation and separation method Download PDFInfo
- Publication number
- CN101613621A CN101613621A CN200810115610A CN200810115610A CN101613621A CN 101613621 A CN101613621 A CN 101613621A CN 200810115610 A CN200810115610 A CN 200810115610A CN 200810115610 A CN200810115610 A CN 200810115610A CN 101613621 A CN101613621 A CN 101613621A
- Authority
- CN
- China
- Prior art keywords
- carbon
- hydrogenation
- logistics
- rich
- tower
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Abstract
Splitting gas disclosed by the invention selects hydrogenation and isolating method to belong to the technical field of unsaturated hydrocarbon selective hydrogenation, for the liquid phase stream that solves the mixed phase hydrogenator that exists in the prior art contains a large amount of carbon three and carbon four components, in reactor, can not play washing action fully, and the energy consumption height that repeats to enter the front-end deethanization tower and cause, equipment size is big, running cost is high and be unfavorable for improving problem such as carbon three selectivity, has proposed a kind of at olefin production plant front-end deethanization tower upstream side and adopt the method that carbon two～carbon ten high unsaturated hydrocarbons (alkynes and diolefin) are carried out selective hydrogenation of debutanizing tower tower base stream effect liquid phase stream.This method plays one's part to the full the liquid phase stream of mixed phase hydrogenator, reduces the inlet amount that enters the front-end deethanization tower, cuts down the consumption of energy and facility investment, and helps improving 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 technology 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 as ethane, propane, butane; Also just like the light component of methane, hydrogen and carbon monoxide and boiling point hydro carbons in gasoline-range.The hydro carbons that in the gas phase monoolefine that obtains by these technologies, also contains a certain amount of higher degree of unsaturation, i.e. alkynes and diolefine with two above carbon atoms.Generally speaking, in the logistics that this method obtains, contain 0.5%～5.3% alkynes and diolefine based on alkene.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 splitting gas selection hydrogenation, " front-end hydrogenation " and " back end hydrogenation " three kinds of technologies.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, the polymkeric substance that generates owing to diene polymerization when catalysis selective hydrogenation makes catalyst deactivation very fast, so splitting gas selects the hydrogenation technique technology seldom to use in industry.
Described " front-end hydrogenation " and " back end hydrogenation " are meant alkyne hydrogenation reactor for the demethanizing tower position, 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.
It 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 that back end hydrogenation removes 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 when therefore removing acetylene is regulated carbon two hydrogenation catalysts.In addition and since the purity of ethylene product be subjected to hydrogen import impurity (as CO, methane etc.) influence and the time have fluctuation, downstream ethylene column need establish " crust formula rectifying section ", or second demethanizing tower is set to separate remaining hydrogen and methane.
Front-end hydrogenation removes the alkynes technology and just occurs the 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 characteristics such as big 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 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 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 alkynes easily or operate abnormal phenomenon, these abnormalities are owing to the go into operation susceptibility and the active temperature excursion that is caused of initial stage live catalyst of ethylene unit produces.In addition, hydrogen and methane are to carry out isolatingly in the higher demethanizing tower system of energy consumption, so it is high more to enter the hydrogen content of demethanizing tower, energy consumption is high more.
Chinese patent application CN1098709A (application on May 12nd, 94) discloses a kind of mixed phase front end C 2 acetylene hydrogenation technology.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 the downstream side and the further separating device of predepropanization tower, 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 positioned at its upstream 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 complete hydrogenation of alkynes, 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
3Logistics with light 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, alkynes in the logistics and diolefin cause the coking of tower still easily, and can increase energy consumption.4,, also need add a series of equipment with to isolated C because when utilizing this patent application technology
3And C
3Above component removes alkynes in addition respectively and removes diolefin and handle, thereby has increased facility investment and production energy consumption on the whole.
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, enter predepropanization tower or front-end deethanization tower then, the liquid phase stream part of tower still loops back the mixed phase hydrogenator and washes beds as liquid phase stream.This patented technology can reduce the reaction unit number of the complete hydrogenation of alkynes, 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 preceding ethane tower, reduce tower still coking amount and reduce energy consumption.But this patented technology also exists problem, for example, uses the liquid phase stream of the liquid phase stream of predepropanization tower or the extraction of preceding ethane Tata still as the 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 a gas phase, they can not play the flushing beds fully, they repeat to enter predepropanization tower or preceding ethane tower simultaneously, and this has increased energy consumption, equipment size and the running cost of predepropanization tower or preceding 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 of being used for selects hydrogenation and isolating method from the splitting gas of olefin production plant, and this 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 still 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 be used for handling contain 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, this 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
3Reach the more liquid phase stream of heavy constituent;
(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 heavy constituent, be rich in C
3Logistics deliver to the propylene refining unit;
(4) step (3) is obtained be rich in carbon four and more the logistics of heavy constituent deliver to debutanizing tower, be separated into the logistics that is rich in C-4-fraction and comprise carbon five and the more logistics of heavy constituent, the logistics circulation that a part is comprised carbon five and more heavy constituent enters mixed phase hydrogenator, remainder extraction.
Described splitting gas from olefin hydrocarbon apparatus preferably flows from the product of steam cracking device or cat-cracker.
Described splitting gas preferred package hydrogen, methane, carbon monoxide, acetylene, ethene, ethane, propylene, propane, butylene, butine, 1,3-butadiene, butane, C from olefin hydrocarbon apparatus
5Non-aromatics, C
6Non-aromatics, C
7Non-aromatics, C
8Non-aromatics, benzene, toluene, vinylbenzene or their mixture.
Preferred described mixed phase hydrogenation reaction and is operated 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.
Described gas phase hydrogenation catalyzer 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.
Preferred described gas phase hydrogenation 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.
The preferred splitting gas of the present invention is selected hydrogenation and isolating method, 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 high unsaturated hydrocarbons 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 cooling back logistics, is separated into and is rich in C
2And more light constituent gaseous stream and be rich in C
3Reach the more liquid phase stream of heavy constituent, said front-end deethanization tower is operated 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
3And more the liquid phase stream of heavy constituent is delivered to depropanizing tower, is separated into the logistics that is rich in carbon three and is rich in carbon four and the more logistics of heavy constituent, and the propylene refining unit is delivered in the logistics that is rich in carbon three;
F. with described be rich in carbon four and more the logistics of heavy constituent deliver to debutanizing tower, be separated into the logistics that is rich in carbon four and comprise carbon five and the more logistics of heavy constituent, mixed phase hydrogenator, remainder extraction are sent in the logistics circulation that a part is comprised carbon five and more heavy constituent;
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 catalyzer preferably at present.Group VIII metal hydrogenation catalyzer the most generally uses, and is catalyzer preferably at present.The group VIII metal loads on a kind of carrier, 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 to be the palladium catalyst of carrier with the aluminum oxide, see US patent US-3679762 and U.S. Pat-4762956; Also have with TiO
2Be the palladium catalyst of carrier, see U.S. Pat-4839329; With SiO
2Be the palladium-zinc catalyst of carrier, see German patent application DE-A2156544; With CaCO
3Palladium-plumbous catalyzer for carrier; 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 activity of such catalysts component, prior art also comprises the palladium catalyst that adds promotor, U.S. Pat 4,404, and 124 disclosed promotors are silver; The disclosed promotor of European patent application EP-A892252 is a gold; German patent application DE-A1284403 and U.S. Pat 4,577,047 disclosed promotor are chromium; U.S. Pat 3,912,789 disclosed promotors are copper; U.S. Pat 3,900,526 disclosed promotors are iron; U.S. Pat 3,489,809 disclosed promotors are rhodium; U.S. Pat 3,325,556 disclosed promotors are lithium; The disclosed promotor of Chinese patent application CN 1151908A is a potassium.In addition, U.S. Pat-4571442; U.S. Pat-4347392; U.S. Pat-4128595; U.S. Pat-5059732 and U.S. Pat-5414170 also discloses the catalyst component and the technology of alkynes and selective hydrogenation of diolefin as.
Above mentioned patent, patent application and publication all introduce as reference of the present invention in full.
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 hydrogenation of all basically 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 cat head vapor phase stream that can make the front-end deethanization tower is directly carried 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 is meant at beds and has gas phase and two kinds of logistics of liquid phase.
The liquid phase material (it consist of carbon five and more heavy constituent) of the present invention at the bottom of with preceding debutylize Tata 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 the 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, make 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 the equipment size and the running cost of front-end deethanization tower, help improving the selectivity of carbon three hydrogenation simultaneously.
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, not only can clean or the refrigerative advantage the mixed phase hydrogenator, can also be to comprising the C of acetylene
2～C
10High unsaturated hydrocarbons carries out selective hydrogenation, has enlarged the hydrogenation scope greatly.
In addition, the contriver unexpectedly finds can significantly reduce the coking amount of tower still, and cut down the consumption of energy because logistics has removed a large amount of high unsaturated hydrocarbons before entering the front-end deethanization tower.
The present invention can reduce the reaction unit number of the complete hydrogenation of alkynes, 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 tower still coking amount and reduces energy consumption.
Description of drawings
Fig. 1 is the synoptic diagram that expression splitting gas of the present invention is selected hydrogenation and isolating method.
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 splitting gas selection hydrogenation of the present invention and isolating method below in conjunction with accompanying drawing.
The olefin production plant C that is used for of the present invention
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
3Reach the more liquid phase stream of heavy constituent;
(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 heavy constituent, be rich in C
3Logistics deliver to carbon three hydrogenators 6;
(4) step (3) is obtained be rich in carbon four and more the logistics of heavy constituent deliver to debutanizing tower 4, be separated into the logistics that is rich in C-4-fraction and comprise carbon five and the more logistics of heavy constituent, the logistics circulation that a part is comprised carbon five and more heavy constituent enters mixed phase hydrogenator 1, remainder extraction.
Preferably, the splitting gas that is used for olefin production plant of the present invention selects hydrogenation and isolating method to preferably include following steps:
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 cooling back logistics, is separated into and is rich in C
2And more light constituent gaseous stream and be rich in C
3Reach the more liquid phase stream of heavy constituent, said front-end deethanization tower 2 is operated 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
3And more the liquid phase stream of heavy constituent is delivered to depropanizing tower 3, is separated into the logistics that is rich in carbon three and is rich in carbon four and the more logistics of heavy constituent, and carbon three hydrogenators 6 are delivered in the logistics that is rich in carbon three;
F. with described be rich in carbon four and more the logistics of heavy constituent deliver to debutanizing tower 4, be separated into the logistics that is rich in carbon four and comprise carbon five and the more logistics of heavy constituent, mixed phase hydrogenator 1, remainder extraction are sent in the logistics circulation that a part is comprised carbon five and more heavy constituent;
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, carries out heat exchange then in heat exchanger, enters mixed phase hydrogenator 1.Mixed phase hydrogenator 1 is in low relatively 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%.The reaction product of coming out from the mixed phase hydrogenator, 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), and the temperature and pressure condition of employing 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.The effluent that comes out from carbon two front-end hydrogenation reactors 5 is through the heat exchanger partial condensation, gas-liquid separation in separating tank, and liquid phase is delivered to the front-end deethanization column overhead as the backflow of front-end deethanization tower 2, and 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,, enter in carbon three hydrogenators 6 (catalyzer that uses is produced as the Beijing Chemical Institute of China Petrochemical Corporation) through heat exchanger heats.This area that operates in of depropanizing tower and carbon three hydrogenators is a mature technology, repeats no more here.Logistics from the depropanizing tower still enters debutanizing tower, be separated into carbon four logistics and comprise carbon five and the more logistics of heavy constituent, a part comprise carbon five and more the logistics of heavy constituent turn back to mixed phase hydrogenator 1, the rest part extraction.
Because the concrete operations parameter is influenced by each unitary controlling index and pressure, temperature and flow etc. influence each other, 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 influence 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 is formed (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. one kind is used for splitting gas selection hydrogenation and isolating method, 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
3Reach the more liquid phase stream of heavy constituent;
(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 heavy constituent, be rich in C
3Logistics deliver to the propylene refining unit;
(4) step (3) is obtained be rich in carbon four and more the logistics of heavy constituent deliver to debutanizing tower, be separated into the logistics that is rich in C-4-fraction and comprise carbon five and the more logistics of heavy constituent, the logistics circulation that a part is comprised carbon five and more heavy constituent enters mixed phase hydrogenator, remainder extraction.
2. the method for claim 1, wherein said splitting gas from olefin hydrocarbon apparatus are 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 is operated 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, wherein said gas phase hydrogenation catalyzer 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, wherein said gas phase hydrogenation 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.
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 high unsaturated hydrocarbons 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 cooling back logistics, is separated into and is rich in C
2And more light constituent gaseous stream and be rich in C
3Reach the more liquid phase stream of heavy constituent, said front-end deethanization tower is operated 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
3And more the liquid phase stream of heavy constituent is delivered to depropanizing tower, is separated into the logistics that is rich in carbon three and is rich in carbon four and the more logistics of heavy constituent, and the propylene refining unit is delivered in the logistics that is rich in carbon three;
F. with described be rich in carbon four and more the logistics of heavy constituent deliver to debutanizing tower, be separated into the logistics that is rich in carbon four and comprise carbon five and the more logistics of heavy constituent, mixed phase hydrogenator, remainder extraction are sent in the logistics circulation that a part is comprised carbon five and more heavy constituent;
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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200810115610 CN101613621B (en) | 2008-06-26 | 2008-06-26 | Method for selective hydrogenation and separation for pyrolysis gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200810115610 CN101613621B (en) | 2008-06-26 | 2008-06-26 | Method for selective hydrogenation and separation for pyrolysis gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101613621A true CN101613621A (en) | 2009-12-30 |
| CN101613621B CN101613621B (en) | 2013-02-06 |
Family
ID=41493512
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200810115610 Active CN101613621B (en) | 2008-06-26 | 2008-06-26 | Method for selective hydrogenation and separation for pyrolysis gas |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101613621B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102220168A (en) * | 2010-04-13 | 2011-10-19 | 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 |
| CN102408916A (en) * | 2010-09-21 | 2012-04-11 | 中国石油化工股份有限公司 | Method for removing alkine and dialkene from pyrolysis gas through selective hydrogenation |
| CN102924218A (en) * | 2012-11-09 | 2013-02-13 | 北京斯伯乐科学技术研究院 | Multifunctional antioxidant for benzene preparing device and using method thereof |
| CN105732280A (en) * | 2014-12-12 | 2016-07-06 | 中国石油天然气股份有限公司 | Front-deethanization front-hydrogenation method for C2 fraction |
| CN107970927A (en) * | 2016-10-24 | 2018-05-01 | 中国石油化工股份有限公司 | Selective hydrogenation of pyrolysis gas catalyst, preparation method and method of hydrotreating |
| CN114471375A (en) * | 2020-10-23 | 2022-05-13 | 中国石油化工股份有限公司 | Apparatus and method for fully hydrogenating mixed C4 stream |
-
2008
- 2008-06-26 CN CN 200810115610 patent/CN101613621B/en active Active
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102220168A (en) * | 2010-04-13 | 2011-10-19 | 中国石油化工股份有限公司 | Method for selective hydrogenation of pyrolysis gas |
| 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 |
| CN102408916A (en) * | 2010-09-21 | 2012-04-11 | 中国石油化工股份有限公司 | Method for removing alkine and dialkene from pyrolysis gas through selective hydrogenation |
| CN102924218A (en) * | 2012-11-09 | 2013-02-13 | 北京斯伯乐科学技术研究院 | Multifunctional antioxidant for benzene preparing device and using method thereof |
| 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 |
| CN105732280A (en) * | 2014-12-12 | 2016-07-06 | 中国石油天然气股份有限公司 | Front-deethanization front-hydrogenation method for C2 fraction |
| CN105732280B (en) * | 2014-12-12 | 2017-12-19 | 中国石油天然气股份有限公司 | C-2-fraction front-end deethanization front-end hydrogenation method |
| CN107970927A (en) * | 2016-10-24 | 2018-05-01 | 中国石油化工股份有限公司 | Selective hydrogenation of pyrolysis gas catalyst, preparation method and method of hydrotreating |
| 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 |
| CN114471375A (en) * | 2020-10-23 | 2022-05-13 | 中国石油化工股份有限公司 | Apparatus and method for fully hydrogenating mixed C4 stream |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101613621B (en) | 2013-02-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1109090C (en) | Selective hydrogenation process of mixed hydrocarbono as prefraction with high unsaturation of C2-C10 | |
| CN101818077B (en) | Selective hydrogenation method of highly unsaturated hydrocarbons in cracking gas | |
| CN101450884B (en) | High unsaturated hydrocarbon selective hydrogenation method in cracking gas | |
| KR101105308B1 (en) | Process for the selective hydrogenation of alkynes and/or dienes in an olefin-containing hydrocarbon stream | |
| CN101613621B (en) | Method for selective hydrogenation and separation for pyrolysis gas | |
| CN109485536B (en) | Selective hydrogenation method for alkyne and/or diene in carbon four fraction | |
| CN101451077B (en) | Selective hydrogenation method of acetylene hydrocarbon and dialkene in cracking gas | |
| CN104250194B (en) | A kind of preparation method of iso-butylene | |
| CN102285860B (en) | Selective hydrogenation process for C4 material flow with high concentration of alkyne | |
| EP3331844B1 (en) | Method for hydrogenation of alkenes and alkynes in low pressure hydrocarbons process streams | |
| CN108017499A (en) | A kind of utilization system and method for comprehensive utilization of methanol to olefins reaction product | |
| CN109485535B (en) | Full hydrogenation method for unsaturated hydrocarbon in four-carbon fraction | |
| CN101423452B (en) | Selective hydrogenation method for fore-fraction high unsaturated hydrocarbons mixed phase | |
| CN103146428B (en) | A kind of full hydrogenation technique of unsaturated hydrocarbons cut | |
| CN109485534B (en) | Tail gas hydrogenation method for butadiene extraction device by DMF (dimethyl formamide) method | |
| CN1274649C (en) | Catalytic distillation process for olefin production device | |
| CN109665933B (en) | Carbon four full-hydrogenation device and full-hydrogenation method | |
| CN103121905A (en) | Recovery method of hydrocarbon fuel gas rich in alkyne | |
| CN101844959B (en) | Method for selective hydrogenation between cracked gas compression sections | |
| CN114471375B (en) | Device and method for fully hydrogenating mixed C4 material flow | |
| CN109485538B (en) | Selective hydrogenation method for alkyne in carbon four fraction | |
| CN117945837A (en) | Method and system for producing propylene-containing material flow by using C4-C8 olefins | |
| JP2024517178A (en) | Upgrading of streams containing C3 and C4 hydrocarbons | |
| CN103483121B (en) | Method of preparing butadiene from gasoline | |
| CN115710153A (en) | Carbon four-alkyne hydrogenation method and device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |