CN101423452B - Selective hydrogenation method for fore-fraction high unsaturated hydrocarbons mixed phase - Google Patents
Selective hydrogenation method for fore-fraction high unsaturated hydrocarbons mixed phase Download PDFInfo
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Abstract
The invention discloses a method for mixed-phase selective hydrogenation of front-end volatiles, namely high unsaturated hydrocarbons, which belongs to the technical field of selective hydrogenation of unsaturated hydrocarbons. To solve the problems in the prior art that a liquid phase flow of a mixed phase hydrogenation reactor contains a large quantity of C3, C4 and C5 compositions, fails to fully play a role in washing in the reactor, causes high energy consumption, large equipment size, high operating cost and unfavorable improvement of the selectivity of C3 due to repeatedly entering a front-end depropanizer and so on, the invention provides a method for selective hydrogenation to C2-C10 high unsaturated hydrocarbons (acetylene hydrocarbons and diolefins) by adopting the material flow of the tower bottom of a depentanizer to act on the liquid phase flow at the upstream side of an olefin production device, namely the front-end depropanizer. The method ensures that the liquid phase flow of the mixed phase hydrogenation reactor fully plays a role, reduces the charging rate to the front-end depropanizer, reduces 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 the selection method of hydrotreating of alkynes and diolefine in a kind of cleavage product stream of olefin production plant.
Background technology
Only if 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 like 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.What obtain through this method generally speaking, is to contain 0.5%～5.3% alkynes and diolefine in the main logistics with 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 through 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 containing with the divinyl is main C
4Fraction and a small amount of C
5Diolefin, the polymkeric substance that when catalysis selective hydrogenation, generates owing to diene polymerization makes catalyst deactivation very fast, so splitting gas selects the hydrogenation technique technology in industry, seldom to use.
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 through the material (methane and hydrogen) that methanator has been removed carbon monoxide and carbonic acid gas that back end hydrogenation removes alkynes, through selection 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 receive with hydrogen import impurity (like 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 getting into demethanizing tower.Predepropanization front-end hydrogenation technology is with predepropanization cat head material (methane, hydrogen, carbon monoxide, C
2Fraction and C
3Fraction) before getting into demethanizing tower through 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 of initial stage live catalyst of ethylene unit produces with the active temperature excursion that is caused.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 get into the hydrogen content of demethanizing tower, energy consumption is high more.
One Chinese patent application CN1098709A (application on May 12nd, 94) discloses a kind of mixed phase front end C 2 acetylene hydrogenation technology.Introduce this patented claim as a reference in full here.A kind of mixed phase hydrogenator has been adopted in this patented claim, and this reactor drum is positioned at the downstream side and further separating device of predepropanization tower, like 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 upper reaches 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 patented claim is placed on the downstream side of predepropanization tower with the mixed phase hydrogenator, that get into 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 alkynes such as butine, divinyl, so the amounts of hydrogen that consumes is limited; A large amount of remaining hydrogens get into 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 getting into polymerization process, and make the deterioration in physical properties of polymkeric substance.3, because this patented claim is not carried out hydrotreatment to the logistics that gets into 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 patented claim 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 CN1109090C 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 split product from alkene flow into the mixed phase hydrogenator and select hydrogenation, get into 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 of entering predepropanization tower or front-end deethanization tower, deep cooling part; Reduce energy consumption and equipment size; Also can reduce the diolefin content that gets into 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, carbon five components major part are gas phase; They can not play the flushing beds fully; They repeat to get into 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 can the high unsaturated hydrocarbons in the product stream of cracker 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 method that the olefin production plant foreshot is selected hydrogenation that is used for, 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 front-end volatiles.
The present invention provides a kind of product logistics high unsaturated hydrocarbons that is used for olefin production plant to select the method for hydrogenation.More particularly, the present invention thinks over the tower still extraction logistics that adopts a kind of mixed phase hydrogenator, this reactor drum to be positioned at predepropanization tower upstream side and adopt depentanizer 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) raw material from olefin hydrocarbon apparatus gets into the mixed phase hydrogenator, makes the alkynes of carbon two～carbon ten and at least a portion of diolefin carry out the mixed phase hydrogenation reaction;
(2) will deliver to the predepropanization tower from the elute of mixed phase hydrogenator, and separate into and be rich in C
3More the vapor phase stream of light constituent be rich in C
4The liquid phase stream of heavy constituent more;
(3) vapor phase stream that step (2) is obtained is delivered to the gas phase hydrogenation reaction device and is carried out gas phase hydrogenation reaction; The liquid phase stream that step (2) obtains is delivered to depentanizer, separate into the logistics that is rich in carbon four carbon five and be rich in carbon six and the more logistics of heavy constituent;
(4) further disengaging zone is delivered in the logistics that is rich in carbon four carbon five that step (3) is obtained, and the part circulation of being rich in carbon six and the more logistics of heavy constituent that step (3) is obtained gets into mixed phase hydrogenator, remainder extraction.
Described raw material from olefin hydrocarbon apparatus preferably flows from the product of steam cracking device or cat-cracker.Preferably the product from steam cracking device flows.
Described raw material preferred package hydrogen, methane, carbon monoxide, acetylene, ethene, ethane, propylene, propane, butylene, butine, 1,3-butadiene, butane, C from olefin hydrocarbon apparatus
5Non-aromatic hydrocarbons, C
6Non-aromatic hydrocarbons, C
7Non-aromatic hydrocarbons, C
8Non-aromatic hydrocarbons, 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 oxide, silicon oxide, aluminum oxide, zinc oxide, White tin 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 gas phase hydrogenation reaction device is at 30 ℃～200 ℃ temperature and 0.6MPa～4.0MPa pressure, operates containing in the presence of the group VIII metal hydrogenation catalyzer.
Preferred described 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 oxide, silicon oxide, aluminum oxide, zinc oxide, White tin 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 a kind of 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:
The raw material that a. will contain alkene is through 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 carried out selective hydrogenation;
C. will cool off through water cooler from the elute of mixed phase hydrogenator, the predepropanization tower is sent in cooling back logistics, separates into and is rich in C
3More the gaseous stream of light constituent be rich in C
4The liquid phase stream of heavy constituent more, said predepropanization tower is operated under 0.5MPa～2.0MPa pressure;
D. with the said C that is rich in
3More the gaseous stream of light constituent is delivered to the gas phase hydrogenation reaction device, and all wherein contained acetylene are carried out selective hydrogenation,
E. with the said C that is rich in
4More the liquid phase stream of heavy constituent is delivered to depentanizer, separates into the logistics that is rich in carbon four carbon five and is rich in carbon six and the more logistics of heavy constituent;
F. mixed phase hydrogenator, remainder extraction are sent in said part circulation of being rich in carbon six and the more logistics of heavy constituent;
G. will cool off from the gaseous stream of gas phase hydrogenation reaction device and partial condensation, and the logistics of condensation will be recycled to the top of predepropanization tower as phegma;
H. will deliver to the downstream separation district that comprises demethanizing, ethane or their mixtures from the uncooled gaseous stream of gas phase hydrogenation reaction device.
Any selective hydrogenation catalyst of knowing all can be used in mixed phase of the present invention or the gas phase hydrogenation reaction device.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, like 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 more specifically disclose in document with other catalyzer.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 the palladium catalyst on the cordierite honeycomb carrier of alkali metal containing and/or earth alkali metal, see one 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 one 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, patented claim and publication all introduce as reference of the present invention in full.
According to the present invention, the hydroprocessing condition that in mixed phase or gas phase hydrogenation reaction device, adopts can suitably change according to the composition and property that is processed logistics.Normally; Temperature and pressure will be enough to accomplish the hydrogenation of all basically high unsaturated hydrocarbons contained in the logistics that is fed to the gas phase hydrogenation reaction device; Usually; It is to operate under 0.7MPa～4.0MPa with pressure range that hydrogenation technique is 10 ℃～90 ℃ in TR, and in hydrogenation process, the flow of hydrogen can satisfy at least makes high discord hydrocarbon change into the stoichiometric requirement of monoolefine; And, 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 usually in the scope of about 1～100 mol of hydrogen/1 mole of high unsaturated hydrocarbons.
Thereby can gain enlightenment according to above detailed description for the people who is familiar with present technique the present invention is made various changes.For example, can adopt any known hydrogenation catalyst.And reactor drum 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 predepropanization tower is directly carried out low pressure without compression, and (gas phase hydrogenation reaction of 0.6MPa～1.8MPa) can save compressor like this.
The liquid phase material (it consist of pyrolysis gasoline fraction) of the present invention at the bottom of with preceding depentanize Tata turns back to the mixed phase hydrogenator; Can provide liquid to clean and cooling performance; Remove a large amount of reaction heat; Reactor drum can be simulated a kind of isothermal reactor, improves the selectivity and the security of hydrogenation, improves catalyst life.Compare with Chinese patent CN 1109090C; Basically do not contain carbon three, carbon four and carbon five components in this liquid phase material; Avoid carbon three, carbon four and carbon five components in mixed phase hydrogenator and predepropanization tower, to circulate, make this liquid phase material can play predictive role fully, can reduce the inlet amount that gets into the predepropanization tower simultaneously; Reduce energy consumption and the equipment size and the running cost of predepropanization tower, help improving the selectivity of carbon three hydrogenation simultaneously.
The contriver finds through at predepropanization tower upstream side the mixed phase hydrogenator being set; And the mixed phase hydrogenator is introduced in the liquid phase stream circulation of preceding pentanizer; 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 getting into the predepropanization tower.
The present invention can reduce the reaction unit number of the complete hydrogenation of alkynes, to reduce the hydrogen content that gets into predepropanization tower, deep cooling part, reduces energy consumption and equipment size.The present invention also can reduce the diolefin content that gets into the predepropanization tower, reduces tower still coking amount and reduces energy consumption.
Description of drawings
Fig. 1 is the synoptic diagram that expression foreshot mixed phase of the present invention is selected the method for hydrogenation.
Nomenclature:
1 raw material from olefin hydrocarbon apparatus; 2 mixed phase hydrogenators; 3 logistics from the mixed phase hydrogenator; 4 predepropanization towers; 5 are rich in carbon three and the more logistics of light constituent; 6 are rich in carbon four and the more logistics of heavy constituent; 7 gas phase hydrogenation reaction devices; 8 logistics from the gas phase hydrogenation reaction device; 9 are rich in the logistics of carbon four carbon five; 10 depentanizers; The carbon six of 11 extraction and the more logistics of heavy constituent; 12 loop back the carbon six of mixed phase hydrogenator and the more logistics of heavy constituent.
Embodiment
Further explain the method for foreshot high unsaturated hydrocarbons mixed phase selection hydrogenation of the present invention 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) raw material 1 from olefin hydrocarbon apparatus gets into mixed phase hydrogenator 2, makes the alkynes of carbon two～carbon ten and at least a portion of diolefin carry out the mixed phase hydrogenation reaction;
(2) will deliver to predepropanization tower 4 from the elute 3 of mixed phase hydrogenator 2, and separate into and be rich in C
3More the vapor phase stream 5 of light constituent be rich in C
4The liquid phase stream 6 of heavy constituent more;
(3) vapor phase stream 5 that step (2) is obtained is delivered to gas phase hydrogenation reaction device 7 and is carried out gas phase hydrogenation reaction; The liquid phase stream 6 that step (2) obtains is delivered to depentanizer 10, separate into the logistics 9 that is rich in carbon four carbon five and be rich in the logistics 11,12 of carbon six and more heavy constituent;
(4) further disengaging zone is delivered in the logistics 9 that is rich in carbon four carbon five that step (3) is obtained, and a part that is rich in carbon six and the more logistics of heavy constituent 12 circulations that step (3) is obtained get into mixed phase hydrogenator, remainder 11 extraction.
Preferably, the olefin production plant C that is used for of the present invention
2～C
10High unsaturated hydrocarbons selects the method for hydrogenation to preferably include following steps:
The raw material 1 that a. will contain alkene is through heat exchanger cooling to 10 ℃～100 ℃;
B. will send into mixed phase hydrogenator 2 from the material of step a, at least wherein part high unsaturated hydrocarbons carried out selective hydrogenation;
C. will cool off through water cooler from the elute of mixed phase hydrogenator 3, predepropanization tower 4 is sent in cooling back logistics, separates into and is rich in C
3More the gaseous stream 5 of light constituent be rich in C
4The liquid phase stream 6 of heavy constituent more, said predepropanization tower 4 is operated under 0.5MPa～2.0MPa pressure;
D. with the said C that is rich in
3More the gaseous stream 5 of light constituent is delivered to the gas phase hydrogenation reaction device, and all wherein contained acetylene are carried out selective hydrogenation,
E. with the said C that is rich in
4More the liquid phase stream 6 of heavy constituent is delivered to depentanizer 10, separates into the logistics 9 that is rich in carbon four carbon five and is rich in the logistics 11,12 of carbon six and more heavy constituent;
F. mixed phase hydrogenator, remainder 11 extraction are sent in a said part 12 circulations of being rich in carbon six and the more logistics of heavy constituent;
G. will cool off and partial condensation from the gaseous stream 8 of gas phase hydrogenation reaction device 7, and the logistics of condensation is recycled to the top of predepropanization tower 4 as phegma;
H. will deliver to the downstream separation district that comprises demethanizing, ethane or their mixtures from the uncooled gaseous stream of gas phase hydrogenation reaction device 7.
Embodiment 1
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 12 of coming at the bottom of the past depentanizer with reference to following table, in heat exchanger, carries out heat exchange then, enters mixed phase hydrogenator 2.Mixed phase hydrogenator 2 is in low relatively TR (about 30 ℃～100 ℃) and medium relatively 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%.Reaction product from the mixed phase hydrogenator comes out through the supercooler cooling, gets into predepropanization tower 4, separates into a kind of liquid phase stream 6 and vapor phase stream 5.Liquid phase stream 6 gets into depentanizer 10.Depropanizing tower 4 isolated gaseous streams 5 are extracted out in the past, through heat exchanger heats, enter in the gas phase hydrogenation reaction device 7.The gas phase hydrogenation catalyzer is BC-H-22A hydrogenation catalyst (Beijing Chemical Institute of China Petrochemical Corporation's production), and the temperature and pressure condition that gas phase hydrogenation reaction device 7 adopts will be enough to entering all acetylene hydrogenations in the gas phase hydrogenation reaction device.The BC-H-22A hydrogenation catalyst is ripe the application in industry.Say that generally hydrogenation temperature is 30 ℃～200 ℃, pressure is 1.0MPa～4.0MPa.The elute that comes out from gas phase hydrogenation reaction device 7 is through the heat exchanger partial condensation; Gas-liquid separation in separating tank; Liquid phase is delivered to the predepropanization column overhead as the backflow of predepropanization tower 4, and demethanizing tower and/or deethanizing column that gas phase gets into cooler downstream are used for further separating the separating device of each component with other.
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 confirm these parameters according to concrete practical situation in addition; Therefore present embodiment does not provide the concrete operations parameter; Here it is just passable to provide scope, and this does not influence the enforcement of present embodiment.Usually also be in a scope, to operate in the industry, rather than at a point operation, according to the hydrogenation result, operator can in time change operating parameters.
The table 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-aromatic hydrocarbons | 2.65 |
| Ethene | 28.1 | Benzene | 6.9 |
| Acetylene | 0.8 | Toluene | 3.1 |
| Propane | 0.25 | YLENE | 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 olefin production plant C
2～C
10High unsaturated hydrocarbons is selected the method for hydrogenation, may further comprise the steps:
(1) raw material from olefin hydrocarbon apparatus gets into the mixed phase hydrogenator, makes the alkynes of carbon two～carbon ten and at least a portion of diolefin carry out the mixed phase hydrogenation reaction;
(2) will deliver to the predepropanization tower from the elute of mixed phase hydrogenator, and separate into and be rich in C
3More the vapor phase stream of light constituent be rich in C
4The liquid phase stream of heavy constituent more;
(3) vapor phase stream that step (2) is obtained is delivered to the gas phase hydrogenation reaction device and is carried out gas phase hydrogenation reaction; The liquid phase stream that step (2) obtains is delivered to depentanizer, separate into the logistics that is rich in carbon four carbon five and be rich in carbon six and the more logistics of heavy constituent;
(4) further disengaging zone is delivered in the logistics that is rich in carbon four carbon five that step (3) is obtained, and the part circulation of being rich in carbon six and the more logistics of heavy constituent that step (3) is obtained gets into mixed phase hydrogenator, remainder extraction.
2. the method for claim 1, wherein said raw material from olefin hydrocarbon apparatus are the product stream from steam cracking device or cat-cracker.
3. the method for claim 1, wherein said raw material from olefin hydrocarbon apparatus comprises hydrogen, methane, carbon monoxide, acetylene, ethene, ethane, propylene, propane, butylene, butine, 1,3-butadiene, butane, C
5Non-aromatic hydrocarbons, C
6Non-aromatic hydrocarbons, C
7Non-aromatic hydrocarbons, C
8Non-aromatic hydrocarbons, 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 oxide, silicon oxide, aluminum oxide, zinc oxide, White tin 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 gas phase hydrogenation reaction device 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 oxide, silicon oxide, aluminum oxide, zinc oxide, White tin 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 raw material that a. will contain alkene is through 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 carried out selective hydrogenation;
C. will cool off through water cooler from the elute of mixed phase hydrogenator, the predepropanization tower is sent in cooling back logistics, separates into and is rich in C
3More the gaseous stream of light constituent be rich in C
4The liquid phase stream of heavy constituent more, said predepropanization tower is operated under 0.5MPa～2.0MPa pressure;
D. with the said C that is rich in
3More the gaseous stream of light constituent is delivered to the gas phase hydrogenation reaction device, and wherein contained acetylene is carried out selective hydrogenation,
E. with the said C that is rich in
4More the liquid phase stream of heavy constituent is delivered to depentanizer, separates into the logistics that is rich in carbon four carbon five and is rich in carbon six and the more logistics of heavy constituent;
F. mixed phase hydrogenator, remainder extraction are sent in said part circulation of being rich in carbon six and the more logistics of heavy constituent;
G. will cool off from the gaseous stream of gas phase hydrogenation reaction device and partial condensation, and the logistics of condensation will be recycled to the top of predepropanization tower as phegma;
H. will deliver to the downstream separation district that comprises demethanizing, ethane or their mixtures from the uncooled gaseous stream of gas phase hydrogenation reaction device.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102795954B (en) * | 2011-05-24 | 2015-04-15 | 中国石油化工股份有限公司 | Selective hydrogenation method for long-chain diene |
| CN105732279B (en) * | 2014-12-12 | 2018-06-01 | 中国石油天然气股份有限公司 | C-2-fraction back end hydrogenation method |
| 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 |
| 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1330131A (en) * | 2000-06-15 | 2002-01-09 | 中国石油化工股份有限公司 | Selective hydrogenation process of mixed hydrocarbono as prefraction with high unsaturation of C2-C10 |
| CN1690028A (en) * | 2004-04-22 | 2005-11-02 | 中国石油化工股份有限公司 | Catalytic distillation process for olefin production device |
| CN1809521A (en) * | 2003-06-23 | 2006-07-26 | 切弗朗菲利普化学公司 | Selective hydrocarbon hydrogenation catalyst and process |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1330131A (en) * | 2000-06-15 | 2002-01-09 | 中国石油化工股份有限公司 | Selective hydrogenation process of mixed hydrocarbono as prefraction with high unsaturation of C2-C10 |
| CN1809521A (en) * | 2003-06-23 | 2006-07-26 | 切弗朗菲利普化学公司 | Selective hydrocarbon hydrogenation catalyst and process |
| CN1690028A (en) * | 2004-04-22 | 2005-11-02 | 中国石油化工股份有限公司 | Catalytic distillation process for olefin production device |
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