CN114471375A - Apparatus and method for fully hydrogenating mixed C4 stream - Google Patents

Apparatus and method for fully hydrogenating mixed C4 stream Download PDF

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CN114471375A
CN114471375A CN202011147995.6A CN202011147995A CN114471375A CN 114471375 A CN114471375 A CN 114471375A CN 202011147995 A CN202011147995 A CN 202011147995A CN 114471375 A CN114471375 A CN 114471375A
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mixed
selective hydrogenation
stream
hydrogen
active component
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CN114471375B (en
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杨士芳
刘俊杰
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
    • C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
    • C07C5/05—Partial hydrogenation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
    • C07C5/08—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds
    • C07C5/09—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds to carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
    • C07C7/163—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation
    • C07C7/167—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation for removal of compounds containing a triple carbon-to-carbon bond
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/32—Selective hydrogenation of the diolefin or acetylene compounds

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Abstract

The invention relates to the technical field of petrochemical industry, in particular to a device and a method for fully hydrogenating a mixed C4 material flow. The device for fully hydrogenating the mixed C4 material flow adopts a separating wall tower which is provided with an external condensation and is divided into a selective hydrogenation area and a full hydrogenation area, the selective hydrogenation area and the full hydrogenation area are limited to be separated by a partition plate, the condenser is arranged outside the shell and above the selective hydrogenation area, and selective hydrogenation reaction, material separation and full hydrogenation reaction are integrated in one reactor, so that the process flow is simplified, the retention time of the material is shortened, the equipment investment is saved, and the operation safety is improved. Meanwhile, the method effectively improves the content and selectivity of C4 alkane in the C4 alkane material.

Description

Apparatus and method for fully hydrogenating mixed C4 stream
Technical Field
The invention relates to the technical field of petrochemical industry, in particular to a device and a method for fully hydrogenating a mixed C4 material flow.
Background
The ethylene preparation by hydrocarbon high-temperature steam cracking can produce a byproduct mixed carbon IV, wherein the cracked mixed carbon IV contains a large amount of 1, 3-butadiene, a small amount of Vinyl Acetylene (VA) and Ethyl Acetylene (EA). In order to obtain high purity 1, 3-butadiene, which meets polymer grade requirements or higher, it is necessary to subject the C4 stream to a de-acetylenic treatment. The industrial process is mainly used for refining butadiene products by two-stage solvent extraction and rectification and one-stage direct and rapid process. The alkyne separated contains 10-20 wt% of 1, 3-butadiene in addition to 20-40 wt% of VA and EA, and the material is the so-called high alkyne C4 tail gas.
In industrial production, due to the consideration of safety factors, the carbon four-fraction is generally diluted and then used as a torch for treatment or used as civil liquefied gas, and acetylene hydrocarbon is incompletely combusted, so that the environment pollution is caused. In addition, with the increase of the weight change and the cracking depth of the cracking raw material, the alkyne content in the C4 material flow is higher and higher, the weight fraction of VA exceeds 2%, the load of a secondary extraction system is increased by adopting the traditional two-stage solvent extraction rectification process, the energy consumption is increased, the butadiene loss is increased, and the economic efficiency is reduced.
Another method for removing alkynes is to perform selective hydrogenation to convert alkynes in the C4 stream into butadiene, butenes and a small amount of butanes, the hydrogenation is exothermic, and a large amount of heat is generated during the reaction process, which causes the reactor temperature to rise sharply. In addition, butadiene and other substances in the C4 material flow are extremely unstable, polymerization reaction can occur on the catalyst, so that the catalyst is blocked and deactivated, and the deposition speed of the polymer is further accelerated by the rising of the temperature of the reactor, so that the process has safety hazards and the service life of the catalyst is short.
CN101434508A discloses a method for acetylene hydrocarbon selective hydrogenation, which is to directly perform selective hydrogenation on acetylene hydrocarbon-rich residue material after butadiene extraction, convert acetylene hydrocarbon into butadiene and mono-olefin, and return the hydrogenation product to an extraction device to continuously extract butadiene, thereby increasing the yield of butadiene. The hydrogenation reactor adopts an isothermal reactor, so that the problem of reactor temperature rise caused by reaction heat release is avoided. However, the method still aims at recovering 1, 3-butadiene and has higher requirements on the selectivity of the catalyst.
CN1520387A discloses a selective acetylene hydrogenation process capable of producing high quality dienes with very low acetylene content over a long period of time. The process provides a selective hydrogenation reaction zone in which selective hydrogenation catalyst activity is maintained at a high level in one embodiment by contacting the selective hydrogenation catalyst with a polymer solvent, a diene feed and hydrogen while the process unit remains in operation, and in a second experimental embodiment by contacting the selective hydrogenation catalyst off-line with only the polymer solvent and hydrogen. However, the method introduces a polymer solvent, and needs to perform corresponding subsequent removal operation, so that the operation flow is complex.
CN1872819A discloses a counter-current selective hydrogenation method, in which a mixed C4 hydrocarbon raw material and hydrogen gas are respectively fed into a tower from the upper part and the lower part of a counter-current reactor through a distributor, a downward flowing hydrocarbon fraction and an upward flowing hydrogen gas are in counter-current contact on the surface of a catalyst to generate hydrogenation reaction, meanwhile, light impurity gas in the mixed C4 enters a gas phase under the stripping action of the hydrogen gas and flows out from the top of the reactor together with unreacted first hydrogen gas, and a refined mixed C4 product flows out from the bottom of the reactor. The mixed C4 hydrocarbon feedstock referred to in this process is a C4 mixture from an MTBE plant.
Therefore, there is a need for an apparatus and method for the total hydrogenation of a mixed C4 stream.
Disclosure of Invention
The invention aims to overcome the problems that the temperature of a reactor is increased due to a large amount of reaction heat released by hydrogenation reaction in the prior art in the mixed C4 material flow full hydrogenation, the butadiene is caused to generate polymerization reaction, the catalyst is blocked and inactivated, the process flow operation is complex and the like, and provides a device and a method for the mixed C4 material flow full hydrogenation.
In order to achieve the above object, a first aspect of the present invention provides an apparatus for fully hydrogenating a mixed C4 stream, the apparatus comprising: the separation wall tower comprises a shell and a condenser, a partition plate parallel to the central axis of the shell is arranged in the shell, the partition plate is connected with the top of the separation wall tower and the tower wall and is not connected with the bottom of the separation wall tower, and the partition plate divides the interior of the shell into a selective hydrogenation zone and a full hydrogenation zone;
the selective hydrogenation zone is provided with a selective hydrogenation catalyst bed layer and is used for carrying out a selective hydrogenation reaction by countercurrent contact of a mixed C4 material flow containing alkyne and first hydrogen to saturate alkyne into olefin and obtain a selective hydrogenation product; simultaneously, under the stripping action of first hydrogen, separating light components and heavy components from the selective hydrogenation product;
the condenser is arranged outside the shell and above the selective hydrogenation zone and is used for mixing the light components with the unreacted first hydrogen and condensing to obtain a condensate;
the condenser is provided with a condensate outlet which is communicated with a mixed C4 material flow inlet arranged in the selective hydrogenation zone and is used for returning and mixing the condensate into the mixed C4 material flow;
and the full hydrogenation zone is provided with a full hydrogenation catalyst bed layer and is used for contacting a mixture with second hydrogen to perform full hydrogenation reaction to obtain a C4 alkane stream, wherein the mixture contains the heavy components and unreacted unsaturated hydrocarbons in the mixed C4 stream.
In a second aspect, the present invention provides a process for the total hydrogenation of a mixed C4 stream, the process comprising the steps of:
(1) in the presence of a selective hydrogenation catalyst, carrying out countercurrent contact on a mixed C4 material flow containing alkyne and first hydrogen to carry out selective hydrogenation reaction so as to saturate alkyne into olefin and obtain a selective hydrogenation product; simultaneously, under the stripping action of first hydrogen, separating light components and heavy components from the selective hydrogenation product;
(2) said light components are mixed with unreacted first hydrogen and condensed, the resulting condensate is returned and mixed into said mixed C4 stream;
(3) contacting the mixture with a second hydrogen in the presence of a full hydrogenation catalyst to perform a full hydrogenation reaction to obtain a C4 alkane stream, wherein the mixture contains the heavy components and unreacted unsaturated hydrocarbons in the mixed C4 stream;
wherein the method is carried out in the apparatus provided in the first aspect.
Through the technical scheme, the device for mixing C4 material flow full hydrogenation provided by the invention adopts a separation wall tower which is provided with an external condensation and is divided into a selective hydrogenation area and a full hydrogenation area, the selective hydrogenation area and the full hydrogenation area are limited to be separated by a partition plate, the condenser is arranged outside the shell and above the selective hydrogenation area, and selective hydrogenation reaction, material separation and full hydrogenation reaction are integrated in one reactor, so that the process flow is simplified, the retention time of materials is shortened, the equipment investment is saved, and the operation safety is improved.
Meanwhile, the method for fully hydrogenating the mixed C4 material flow adopts a process of firstly carrying out selective hydrogenation and then carrying out full hydrogenation, namely, before the full hydrogenation, alkyne in the mixed C4 material flow is converted into butadiene and/or butene, and simultaneously the condensate is returned to the mixed C4 material flow, so that the content of alkyne in the mixed C4 material flow is reduced, thereby reducing the heat release of the selective hydrogenation reaction, prolonging the service life of a selective hydrogenation catalyst, and further improving the content and the selectivity of C4 alkane by combining with the full hydrogenation reaction.
Drawings
FIG. 1 is a schematic diagram of a device for fully hydrogenating a mixed C4 stream provided by the invention.
Description of the reference numerals
1. Mixing C4 material flow 2, first hydrogen 3, selective hydrogenation catalyst bed layer
4. Tail gas 5, condensate 6 and partition board
7. Second Hydrogen 8, Total hydrogenation catalyst bed 9, C4 alkane stream
I. A dividing wall tower II, a condenser III and a selective hydrogenation zone
IV, total hydrogenation zone
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In the present invention, the "top" of the container referred to in the specification means 0 to 10% of the position of the container from the top to the bottom without specific description; the "upper" portion of the vessel refers to the 0-30% position of the vessel from top to bottom; the "lower part" of the container means 70-100% of the position of the container from top to bottom; the "bottom" of the container refers to 90-100% of the container from top to bottom.
In a first aspect, the present invention provides an apparatus for the total hydrogenation of a mixed C4 stream, the apparatus comprising: the separation wall tower comprises a shell and a condenser, a partition plate parallel to the central axis of the shell is arranged in the shell, the partition plate is connected with the top of the separation wall tower and the tower wall and is not connected with the bottom of the separation wall tower, and the partition plate divides the interior of the shell into a selective hydrogenation zone and a full hydrogenation zone;
the selective hydrogenation zone is provided with a selective hydrogenation catalyst bed layer and is used for carrying out a selective hydrogenation reaction by countercurrent contact of a mixed C4 material flow containing alkyne and first hydrogen to saturate alkyne into olefin and obtain a selective hydrogenation product; simultaneously, under the stripping action of first hydrogen, separating light components and heavy components from the selective hydrogenation product;
the condenser is arranged outside the shell and above the selective hydrogenation zone and is used for mixing the light components with the unreacted first hydrogen and condensing to obtain a condensate;
the condenser is provided with a condensate outlet which is communicated with a mixed C4 material flow inlet arranged in the selective hydrogenation zone and is used for returning and mixing the condensate into the mixed C4 material flow;
and the full hydrogenation zone is provided with a full hydrogenation catalyst bed layer and is used for contacting a mixture with second hydrogen to perform full hydrogenation reaction to obtain a C4 alkane stream, wherein the mixture contains the heavy components and unreacted unsaturated hydrocarbons in the mixed C4 stream.
In the present invention, there is no particular case where one end of the partition is connected to the top of the divided wall column and the other end of the partition is not connected to the bottom of the divided wall column.
In the present invention, the selective hydrogenation products are butadiene and butene, preferably, the butadiene is 1, 3-butadiene and/or 1, 2-butadiene, and the butene is 1-butene and/or 2-butene; the light component is butylene, and the heavy component is butadiene.
In the present invention, the unreacted unsaturated hydrocarbon in the mixed C4 stream refers to the olefin and unreacted alkyne in the mixed C4 stream without special case indication.
According to the present invention, preferably, the selective hydrogenation zone is provided with an inlet for a mixed C4 stream and an inlet for a first hydrogen gas.
To fully embody the countercurrent contacting of the mixed C4 stream with the first hydrogen and to increase the saturation of acetylenes in the mixed C4 stream. Preferably, the mixed C4 stream inlet is disposed above the first hydrogen inlet.
According to the invention, preferably, the height ratio of the bed of selective hydrogenation catalyst to the selective hydrogenation zone is between 0.4 and 0.9:1, preferably 0.6 to 0.8: 1. in the present invention, the height of the selective hydrogenation zone corresponds to the height of the partition, unless otherwise specified. And the optimized conditions are adopted, so that the alkyne in the mixed C4 material flow is more favorably converted into the butadiene and the butene, and the conversion rate of the alkyne is improved.
In some embodiments of the invention, preferably, the bed of selective hydrogenation catalyst is disposed between the inlet of the mixed C4 stream and the first hydrogen inlet.
According to the present invention, preferably, the full hydrogenation zone is further provided with a C4 alkane stream outlet and a second hydrogen inlet.
To enhance the full hydrogenation reaction of the mixture with the second hydrogen gas, preferably, the C4 alkane stream outlet is disposed above the second hydrogen gas inlet.
According to the present invention, preferably, the total hydrogenation zone contains a total hydrogenation catalyst bed, and the height ratio of the total hydrogenation catalyst bed to the total hydrogenation zone is 0.3-0.9: 1, preferably 0.6 to 0.8: 1.
according to a preferred embodiment of the present invention, the full hydrogenation zone catalyst bed is disposed between the C4 alkane stream outlet and the second hydrogen inlet.
Preferably, the ratio of the radius of the selective hydrogenation zone to the radius of the total hydrogenation zone is 0.5-1.5: 1, preferably 0.8 to 1.2: 1. the optimized conditions are adopted, so that the sufficiency of the selective hydrogenation reaction and the full hydrogenation reaction is ensured.
Preferably, the ratio of the height of the partition to the height of the divided wall column is from 0.5 to 0.9:1, preferably 0.7 to 0.9: 1. preferred conditions are used to better facilitate the simultaneous selective hydrogenation of the mixed C4 feed and stripping of the upper hydrogen on the left side of the dividing wall column.
In the present invention, the partition has a wide range of options as long as the partition wall column is partitioned into a selective hydrogenation zone and a butadiene extraction zone.
An apparatus for fully hydrogenating a mixed C4 stream according to the present invention, as shown in fig. 1, comprises: the separation wall tower I comprises a shell and a condenser II, a partition plate 6 parallel to the central axis of the shell is arranged in the shell, the partition plate 6 is connected with the top of the separation wall tower and the tower wall and is not connected with the bottom of the separation wall tower, and the partition plate 6 partitions the interior of the shell into a selective hydrogenation zone III and a total hydrogenation zone IV;
the selective hydrogenation zone III is provided with a selective hydrogenation catalyst bed layer 3 for carrying out a selective hydrogenation reaction by countercurrent contact of a mixed C4 material flow 1 containing alkyne and first hydrogen 2 so as to saturate alkyne into alkene and obtain a selective hydrogenation product; simultaneously, under the stripping action of first hydrogen 1, separating light components and heavy components from the selective hydrogenation product;
the condenser II is arranged outside the shell and above the selective hydrogenation zone III and is used for mixing the light components with the unreacted first hydrogen and condensing to obtain a condensate 5 and a tail gas 4;
the condenser II is provided with a condensate outlet which is communicated with a mixed C4 material flow inlet arranged in the selective hydrogenation zone III and is used for returning and mixing the condensate 5 into the mixed C4 material flow 1;
the total hydrogenation zone IV is provided with a total hydrogenation catalyst bed layer 8 for contacting a mixture with a second hydrogen 7 to perform a total hydrogenation reaction to obtain a C4 alkane stream 9, wherein the mixture contains the heavy components and unreacted unsaturated hydrocarbons in the mixed C4 stream.
Preferably, the selective hydrogenation zone III is further provided with the mixed C4 stream inlet and a first hydrogen inlet, and the bed of selective hydrogenation catalyst 3 is disposed between the mixed C4 stream inlet and the first hydrogen inlet.
Preferably, the total hydrogenation zone IV is further provided with the C4 alkane stream outlet and a second hydrogen inlet, and the total hydrogenation zone catalyst bed 8 is disposed between the C4 alkane stream outlet and the second hydrogen inlet.
In a second aspect, the present invention provides a process for the total hydrogenation of a mixed C4 stream, the process comprising the steps of:
(1) in the presence of a selective hydrogenation catalyst, carrying out countercurrent contact on a mixed C4 material flow containing alkyne and first hydrogen to carry out selective hydrogenation reaction so as to saturate alkyne into olefin and obtain a selective hydrogenation product; simultaneously, under the steam stripping action of first hydrogen, separating light components and heavy components from the hydrogenation product;
(2) said light components are mixed with unreacted first hydrogen and condensed, the resulting condensate is returned and mixed into said mixed C4 stream;
(3) contacting the mixture with a second hydrogen in the presence of a full hydrogenation catalyst to perform a full hydrogenation reaction to obtain a C4 alkane stream, wherein the mixture contains the heavy components and unreacted unsaturated hydrocarbons in the mixed C4 stream;
wherein the method is carried out in the apparatus provided in the first aspect.
The inventor of the invention finds in research that: the method for completely hydrogenating the mixed C4 material flow adopts a process flow of firstly carrying out selective hydrogenation and then carrying out complete hydrogenation, namely acetylene hydrocarbon is converted into butadiene and/or butene before the complete hydrogenation, and the acetylene hydrocarbon is combined with the stripping action and the condensation separation of hydrogen gas, a condensate containing the butene is returned and mixed into the mixed C4 material flow, so that the bed temperature shock caused by the heat release of the selective hydrogenation reaction is reduced by reducing the content of the acetylene hydrocarbon, the generation of polymers and the deposition on the surface of a catalyst are effectively inhibited, and the service lives of a selective hydrogenation catalyst and a complete hydrogenation catalyst are prolonged.
In the present invention, the alkyne refers to a C4 alkyne, unless otherwise specified.
In some embodiments of the present invention, it is preferred that the acetylenes are present in an amount of 20 to 50 wt%, preferably 30 to 40 wt%, based on the weight of the mixed C4 stream. In the present invention, the content of the alkyne is measured by a gas chromatography method.
According to the present invention, preferably, the mixed C4 stream also contains olefins; wherein the olefin is selected from butadiene and/or butene.
In some embodiments of the present invention, it is preferred that the butene content of the olefin is from 5 to 30 wt%, preferably from 5 to 15 wt%, based on the weight of the mixed C4 stream; the butadiene content is from 20 to 40% by weight, preferably from 20 to 30% by weight. In the present invention, the butene and butadiene contents are both measured by a gas chromatography method.
In the present invention, there is a wide selection of sources for the mixed C4 stream, as long as the acetylenic content in the mixed C4 stream is in the range of 20 to 50 wt%. Preferably, the mixed C4 stream is from a butadiene extraction unit and/or a hydrocarbon steam cracking unit. Wherein the hydrocarbon cracking device may be an ethylene cracking device.
According to the present invention, preferably, the alkyne is selected from at least one of methylacetylene, ethylacetylene and vinylacetylene.
In the present invention, the first and second are not particularly limited, but are for distinguishing the same substance from different phases.
Preferably, the molar ratio of the mixed C4 stream to the first hydrogen is 1: 0.5 to 3, preferably 1: 0.5-1.5. Wherein the molar amount of the mixed C4 stream is based on the molar amount of acetylenes in the mixed C4 stream. The preferred conditions are adopted to be more favorable for completely converting the alkynes in the mixed C4 material flow into butadiene and butylene; wherein the butene mainly refers to 1-butene.
In the present invention, there is a wide range of conditions for the selective hydrogenation reaction, as long as the acetylene hydrocarbons in the mixed C4 stream are subjected to the selective hydrogenation reaction to convert into butadiene and butene. Preferably, the conditions of the selective hydrogenation reaction include: the pressure is 0.1-5MPa, preferably 0.6-4 MPa; the temperature is 20-80 ℃, and preferably 30-80 ℃; the volume space velocity is 10-100h-1Preferably 10-50h-1。
According to the present invention, preferably, the selective hydrogenation product is butadiene and/or butene; further preferably, the selectively hydrogenated products are butadiene and butene. Further preferably, the butadiene is selected from 1, 3-butadiene and/or 1, 2-butadiene, preferably 1, 3-butadiene; the butene is selected from 1-butene and/or 2-butene, preferably 1-butene.
In the present invention, the selective hydrogenation catalyst has a wide selection range, so long as the alkyne in the mixed C4 stream and the first hydrogen are subjected to selective hydrogenation reaction. Preferably, the selective hydrogenation catalyst comprises a first active component and a first support.
According to the present invention, preferably, the first active component comprises a first main active component and optionally a first co-active component.
Further preferably, the content of the first main active component is 0.01 to 1.5 wt%, preferably 0.1 to 0.3 wt%, based on the weight of the selective hydrogenation catalyst; the content of the first co-active component is 0-25 wt%, preferably 0-12 wt%.
According to the present invention, preferably, the first main active component is selected from at least one of palladium, rhodium, platinum and nickel, preferably palladium.
In some embodiments of the present invention, preferably, the first active component comprises a first main active component and a first co-active component; further preferably, the first co-active component is selected from lead and/or tin, and optionally at least one of potassium, sodium, lithium, calcium, magnesium, barium, fluorine, copper, silver, gold, zinc, manganese, bismuth, molybdenum, zirconium and rare earth elements; more preferably, the first co-active component contains lead and at least one of potassium, sodium, lithium, calcium, magnesium, barium, fluorine, copper, silver, gold, zinc, manganese, bismuth, molybdenum, zirconium and rare earth elements.
According to a preferred embodiment of the present invention, the first active component of the selective hydrogenation catalyst comprises a first main active component and a first co-active component. Preferably, the first active component is selected from a palladium-lead two-component or a palladium-lead multi-component.
Preferably, the specific surface area of the first support is 1 to 250m2A/g, preferably from 80 to 200m2(ii)/g; the average pore diameter is 5-300nm, preferably 50-200 nm; the pore volume is 0.2-1mL/g, preferably 0.3-0.7 mL/g.
In some embodiments of the present invention, preferably, the first support is selected from at least one of alumina, silica, spinel, diatomaceous earth, titania, zinc oxide, tin oxide, and molecular sieves, preferably alumina.
In the present invention, there is a wide range of choices for the shape of the selective hydrogenation catalyst. Preferably, the shape of the selective hydrogenation catalyst is selected from at least one of a granular shape, a spherical shape, a gear shape, a blade shape and a bar shape.
In the present invention, the selective hydrogenation catalyst can be obtained commercially or prepared; wherein, the preparation method of the selective hydrogenation catalyst is a method well known by the technical personnel in the field.
In the present invention, in step (1), the countercurrent contacting of the mixed alkyne-containing C4 stream with the first hydrogen is intended to increase the efficiency of the selective hydrogenation reaction. Preferably, the inlet of the mixed C4 stream is located above the inlet of the first hydrogen; further preferably, the inlet for the mixed C4 stream is located in the upper portion of the bed of selective hydrogenation catalyst and the inlet for the first hydrogen is located in the lower portion of the bed of selective hydrogenation catalyst.
In the present invention, in step (2), the condensation is intended to separate a mixture of the light components and unreacted first hydrogen to obtain a condensate; preferably, the condensate contains butenes and alkynes.
According to the present invention, preferably, the condensation separation also results in a tail gas, wherein the tail gas contains the first hydrogen, methane, ethane and propane.
According to a preferred embodiment of the invention, the condensate is returned and mixed into the mixed C4 stream, so that the reduction of the content of the alkyne is beneficial to reducing the bed temperature shock caused by the heat release of the selective hydrogenation reaction, the generation of polymers and the deposition on the surface of the selective hydrogenation catalyst are effectively inhibited, and the service life of the selective hydrogenation catalyst is prolonged.
Preferably, the molar ratio of the mixture to the second hydrogen is 1: 0.1 to 6; preferably 1: 0.4-4.5. Wherein the molar amount of the mixture is based on the molar amount of unsaturated hydrocarbons in the mixture.
In the present invention, there is a wide range of choice for the conditions of the total hydrogenation reaction, as long as the unreacted unsaturated hydrocarbons and heavier components in the mixture, i.e., the mixed C4 stream, are converted to saturated alkanes. Preferably, the conditions of the total hydrogenation reaction include: the pressure is 1-10MPa, preferably 1-4 MPa; the temperature is 10-80 ℃, and the preferred temperature is 20-50 ℃; the volume space velocity is 5-100h-1Preferably 10-40h-1。
In the present invention, there is a wide selection range of the total hydrogenation catalyst, and preferably, the total hydrogenation catalyst contains a second active component and a second carrier.
According to the present invention, preferably, the second active component comprises a second main active component and optionally a second co-active component.
Further preferably, the content of the second main active component is 0.01 to 1 wt%, preferably 0.05 to 0.8 wt%, based on the weight of the total hydrogenation catalyst; the content of the second co-active component is 0.001 to 1 wt%, preferably 0.05 to 0.8 wt%.
Further preferably, the second main active component is at least one selected from palladium, rhodium, platinum and nickel, preferably palladium.
In some embodiments of the present invention, preferably, the second active component comprises a second main active component and a second co-active component; further preferably, the second co-active component is selected from at least one of potassium, sodium, lithium, calcium, magnesium, barium, fluorine, copper, silver, gold, lead, tin, zinc, manganese, bismuth, molybdenum, zirconium and rare earth elements, preferably silver.
According to a preferred embodiment of the present invention, the second active component in the total hydrogenation catalyst comprises a second main active component and a second auxiliary active component, and preferably, the second active component is selected from palladium-silver bi-component or palladium-silver multi-component.
Preferably, the specific surface area of the second carrier is 1 to 300m2Per g, preferably 100-2(ii)/g; the average pore diameter is 5-250nm, preferably 50-200 nm; the pore volume is 0.3-1.5mL/g, preferably 0.5-1 mL/g.
Preferably, the second support is selected from at least one of alumina, silica, spinel, diatomaceous earth, titania, zinc oxide, tin oxide and molecular sieves, preferably alumina.
In the present invention, there is a wide range of choices for the shape of the perhydrogenation catalyst. Preferably, the shape of the total hydrogenation catalyst is selected from at least one of a granular shape, a spherical shape, a gear shape, a blade shape and a bar shape.
In the present invention, the perhydrogenation catalyst may be obtained commercially or may be prepared; wherein, the preparation method of the total hydrogenation catalyst is a method well known by the technical personnel in the field.
According to the present invention, preferably, the C4 alkane stream is returned to the cracking furnace as cracking raw material to continue participating in the cracking reaction. In a preferred manner, the utilization of the mixed C4 stream is improved.
According to the present invention, preferably, the C4 alkane stream has a C4 alkane content of 60 to 95 wt%, preferably 80 to 90 wt%.
Preferably, the C4 alkane selectivity of the C4 alkane stream is in the range of 60 to 90%, preferably 70 to 80%.
The present invention will be described in detail below by way of examples.
Example 1
(1) The apparatus for the total hydrogenation of a mixed C4 stream is shown in FIG. 1, i.e., the apparatus comprises: the separation wall tower I comprises a shell and a condenser II, a partition plate 6 parallel to the central axis of the shell is arranged in the shell, the partition plate 6 is connected with the top and the tower wall of the separation wall tower I and is not connected with the bottom of the separation wall tower I, the partition plate 6 partitions the interior of the shell into a selective hydrogenation zone III and a full hydrogenation zone IV, the condenser II is arranged outside the shell and above the selective hydrogenation zone III, and the condenser II is provided with a condensate outlet and is communicated with a mixed C4 material flow inlet arranged in the selective hydrogenation zone III;
the selective hydrogenation zone III is provided with a mixed C4 material flow inlet, a selective hydrogenation catalyst bed layer and a first hydrogen inlet, and the selective hydrogenation catalyst bed layer 3 is arranged between the mixed C4 material flow inlet and the first hydrogen inlet, wherein the height ratio of the selective hydrogenation catalyst bed layer to the selective hydrogenation zone is 0.6: 1;
the full hydrogenation zone IV is provided with a C4 alkane material flow outlet, a full hydrogenation catalyst bed layer and a second hydrogen inlet, and the full hydrogenation zone catalyst bed layer 8 is arranged between the C4 alkane material flow outlet and the second hydrogen inlet, wherein the height ratio of the full hydrogenation catalyst bed layer to the full hydrogenation zone is 0.6: 1;
the radius ratio of the selective hydrogenation zone III to the full hydrogenation zone IV is 1:1, and the height ratio of the partition plate 6 to the partition wall tower I is 0.9: 1.
(2) A process for the total hydrogenation of a mixed C4 stream, the process comprising：
a. In the selective hydrogenation catalyst (active components are palladium and lead, a carrier is alumina, and the weight of the selective hydrogenation catalyst is taken as a reference, the content of the palladium is 0.2 weight percent, the content of the lead is 8 weight percent, and the specific surface area of the alumina is 200m2And/g, the average pore diameter is 250nm, and the pore volume is 0.8mL/g), and the mixed C4 material flow (butadiene extraction device, the content of alkyne is 40 wt%) and first hydrogen are subjected to selective hydrogenation reaction according to the molar ratio of 1:2, wherein the conditions of the selective hydrogenation reaction comprise: the pressure is 1.6MPa, the temperature is 30 ℃, and the volume space velocity is 50h-1To obtain selective hydrogenation products; simultaneously, under the steam stripping action of first hydrogen, separating light components and heavy components from the hydrogenation product;
b. said light components are mixed with unreacted first hydrogen and condensed, the resulting condensate is returned and mixed into said mixed C4 stream;
c. in the full hydrogenation catalyst (active components are palladium and silver, a carrier is alumina, and the weight of the selective hydrogenation catalyst is taken as a reference, the content of the palladium is 0.1 wt%, the content of the silver is 0.2 wt%, and the specific surface area of the alumina is 250m2Per g, average pore diameter of 150nm and pore volume of 1mL/g), and carrying out full hydrogenation reaction on a mixture and a second hydrogen according to a molar ratio of 1:1.2, wherein the mixture contains unreacted unsaturated hydrocarbon and heavy components in a mixed C4 flow, and the conditions of the full hydrogenation reaction comprise: the pressure is 2.4MPa, the temperature is 35 ℃, and the volume space velocity is 30h-1To obtain C4 alkane stream S1.
Wherein, in the C4 alkane stream S1, the content of C4 alkanes is 88 wt%, and the selectivity of C4 alkanes is 84%.
Example 2
(1) The apparatus for the total hydrogenation of a mixed C4 stream is shown in FIG. 1, i.e., the apparatus comprises: divided wall column I, thereforThe dividing wall tower I comprises a shell and a condenser II, a partition plate 6 parallel to the central axis of the shell is arranged in the shell, the partition plate 6 is connected with the top and the tower wall of the dividing wall tower I and is not connected with the bottom of the dividing wall tower I, the partition plate 6 divides the interior of the shell into a selective hydrogenation zone III and a full hydrogenation zone IV, the condenser II is arranged outside the shell and above the selective hydrogenation zone III, and a condensate outlet is arranged in the condenser II and communicated with a mixed C4 material flow inlet arranged in the selective hydrogenation zone III;
the selective hydrogenation zone III is provided with a mixed C4 material flow inlet, a selective hydrogenation catalyst bed layer and a first hydrogen inlet, and the selective hydrogenation catalyst bed layer 3 is arranged between the mixed C4 material flow inlet and the first hydrogen inlet, wherein the height ratio of the selective hydrogenation catalyst bed layer to the selective hydrogenation zone is 0.7: 1;
the full hydrogenation zone IV is provided with a C4 alkane material flow outlet, a full hydrogenation catalyst bed layer and a second hydrogen inlet, and the full hydrogenation zone catalyst bed layer 8 is arranged between the C4 alkane material flow outlet and the second hydrogen inlet, wherein the height ratio of the full hydrogenation catalyst bed layer to the full hydrogenation zone is 0.8: 1;
the radius ratio of the selective hydrogenation zone III to the full hydrogenation zone IV is 1:1, and the height ratio of the partition plate 6 to the partition wall tower I is 0.9: 1.
(2) A process for the total hydrogenation of a mixed C4 stream, the process comprising:
a. in the selective hydrogenation catalyst (active components are palladium and lead, a carrier is alumina, the weight of the selective hydrogenation catalyst is taken as a reference, the content of the palladium is 0.15 wt%, the content of the lead is 10 wt%, and the specific surface area of the alumina is 180m2And/g, the average pore diameter is 260nm, and the pore volume is 1.5mL/g), and the mixed C4 material flow (butadiene extraction device, the content of alkyne is 30 wt%) and first hydrogen are subjected to selective hydrogenation reaction according to the molar ratio of 1:1, wherein the conditions of the selective hydrogenation reaction comprise: the pressure is 2MPa, the temperature is 50 ℃, and the volume space velocity is 35h-1To obtain selective hydrogenation products; at the same time, in the first hydrogenUnder the steam stripping action of gas, separating light components and heavy components from the hydrogenation product;
b. the light components are mixed with unreacted first hydrogen, the mixed products are condensed and separated, and the obtained condensate is returned and mixed into the mixed C4 material flow;
c. in the full hydrogenation catalyst (active components are palladium and silver, carrier is alumina, and based on the weight of the selective hydrogenation catalyst, the content of the palladium is 0.4 wt%, the content of the silver is 0.3 wt%, and the specific surface area of the alumina is 280m2Per g, average pore diameter of 200nm and pore volume of 0.7mL/g), and a second hydrogen gas in a molar ratio of 1:3, wherein the mixture contains unreacted unsaturated hydrocarbon and heavy components in the mixed C4 stream, and the conditions of the full hydrogenation reaction comprise: the pressure is 3MPa, the temperature is 50 ℃, and the volume space velocity is 25h-1To obtain C4 alkane stream S2.
Wherein, in the C4 alkane stream S2, the content of C4 alkanes is 80 wt%, and the selectivity of C4 alkanes is 78%.
Example 3
(1) The apparatus for the total hydrogenation of a mixed C4 stream is shown in FIG. 1, i.e., the apparatus comprises: the separation wall tower I comprises a shell and a condenser II, a partition plate 6 parallel to the central axis of the shell is arranged in the shell, the partition plate 6 is connected with the top and the tower wall of the separation wall tower I and is not connected with the bottom of the separation wall tower I, the partition plate 6 partitions the interior of the shell into a selective hydrogenation zone III and a full hydrogenation zone IV, the condenser II is arranged outside the shell and above the selective hydrogenation zone III, and the condenser II is provided with a condensate outlet and is communicated with a mixed C4 material flow inlet arranged in the selective hydrogenation zone III;
the selective hydrogenation zone III is provided with a mixed C4 material flow inlet, a selective hydrogenation catalyst bed layer and a first hydrogen inlet, and the selective hydrogenation catalyst bed layer 3 is arranged between the mixed C4 material flow inlet and the first hydrogen inlet, wherein the height ratio of the selective hydrogenation catalyst bed layer to the selective hydrogenation zone is 0.6: 1;
the full hydrogenation zone IV is provided with a C4 alkane material flow outlet, a full hydrogenation catalyst bed layer and a second hydrogen inlet, and the full hydrogenation zone catalyst bed layer 8 is arranged between the C4 alkane material flow outlet and the second hydrogen inlet, wherein the height ratio of the full hydrogenation catalyst bed layer to the full hydrogenation zone is 0.7: 1;
the radius ratio of the selective hydrogenation zone III to the full hydrogenation zone IV is 1:1, and the height ratio of the partition plate 6 to the partition wall tower I is 0.8: 1.
(2) A process for the total hydrogenation of a mixed C4 stream, the process comprising:
a. in the selective hydrogenation catalyst (active components are palladium and lead, the carrier is alumina, and based on the weight of the selective hydrogenation catalyst, the content of the palladium is 0.18 wt%, the content of the lead is 12 wt%, and the specific surface area of the alumina is 100m2In the presence of the catalyst, a mixed C4 material flow (hydrocarbon steam cracking device, the content of alkyne is 35 wt%) and first hydrogen are subjected to selective hydrogenation reaction according to a molar ratio of 1:1.5, wherein the conditions of the selective hydrogenation reaction comprise: the pressure is 3MPa, the temperature is 70 ℃, and the volume space velocity is 50h-1To obtain selective hydrogenation products; simultaneously, under the steam stripping action of first hydrogen, separating light components and heavy components from the hydrogenation product;
b. the light components are mixed with unreacted first hydrogen, the mixed products are condensed and separated, and the obtained condensate is returned and mixed into the mixed C4 material flow;
c. in the full hydrogenation catalyst (active components are palladium and silver, carrier is alumina, and based on the weight of the selective hydrogenation catalyst, the content of the palladium is 0.7 wt%, the content of the silver is 0.6 wt%, and the specific surface area of the alumina is 180m2Per g, average pore diameter of 170nm and pore volume of 0.5mL/g), and a second hydrogen gas in a molar ratio of 1:4, wherein the mixture contains unreacted unsaturated hydrocarbon and heavy components in the mixed C4 stream, and the conditions of the full hydrogenation reaction comprise: the pressure is 3.5MPa, the temperature is 48 ℃, and the volume space velocity is 50h-1To obtain C4 alkane stream S3.
Wherein, in the C4 alkane stream S3, the content of C4 alkane is 85 wt%, and the selectivity of C4 alkane is 80%.
Comparative example 1
Following the procedure of example 1, except omitting step b, C4 paraffin stream D1 was obtained.
Wherein, in the C4 alkane stream D1, the content of C4 alkane is 60 wt%, and the selectivity of C4 alkane is 48%.
Comparative example 2
Following the procedure of example 1 except that in step b, no condensate was returned and mixed into the mixed C4 stream, a C4 paraffinic stream D2 was obtained.
Wherein, in the C4 alkane stream D2, the content of C4 alkane is 50 wt%, and the selectivity of C4 alkane is 36%.
Comparative example 3
The process according to example 1, except that the apparatus for the total hydrogenation of the mixed C4 stream was different from the apparatus shown in fig. 1 and was carried out in a selective hydrogenation reactor and a total hydrogenation reactor, respectively, i.e. a divided wall column without selective hydrogenation zone and total hydrogenation zone, to obtain C4 alkane stream D3.
Wherein, in the C4 alkane stream D3, the content of C4 alkane is 65 wt%, and the selectivity of the C4 alkane is 51%.
It can be seen from the data of the examples and comparative examples that the total hydrogenation apparatus for mixed C4 stream provided by the present invention, i.e. the divided wall column with external condensation and divided into selective hydrogenation zone and total hydrogenation zone, can simultaneously realize selective hydrogenation reaction and total hydrogenation reaction of mixed C4 stream, simplify the operation process, reduce the retention time of the material, increase the content and yield of C4 alkane in the mixed C4 stream, and simultaneously increase the service life of the catalyst.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (10)

1. An apparatus for fully hydrogenating a mixed C4 stream, the apparatus comprising: the separation wall tower comprises a shell and a condenser, a partition plate parallel to the central axis of the shell is arranged in the shell, the partition plate is connected with the top of the separation wall tower and the tower wall and is not connected with the bottom of the separation wall tower, and the partition plate divides the interior of the shell into a selective hydrogenation zone and a full hydrogenation zone;
the selective hydrogenation zone is provided with a selective hydrogenation catalyst bed layer and is used for enabling the mixed C4 material flow containing alkyne to be in countercurrent contact with first hydrogen to carry out selective hydrogenation reaction, so that the alkyne is saturated into olefin, and a selective hydrogenation product is obtained; simultaneously, under the stripping action of first hydrogen, separating light components and heavy components from the selective hydrogenation product;
the condenser is arranged outside the shell and above the selective hydrogenation zone and is used for mixing the light components with the unreacted first hydrogen and condensing to obtain a condensate;
the condenser is provided with a condensate outlet which is communicated with a mixed C4 material flow inlet arranged in the selective hydrogenation zone and is used for returning and mixing the condensate into the mixed C4 material flow;
and the full hydrogenation zone is provided with a full hydrogenation catalyst bed layer and is used for contacting a mixture with second hydrogen to perform full hydrogenation reaction to obtain a C4 alkane stream, wherein the mixture contains the heavy components and unreacted unsaturated hydrocarbons in the mixed C4 stream.
2. The apparatus of claim 1, wherein the selective hydrogenation zone is further provided with a mixed C4 stream inlet and a first hydrogen inlet;
preferably, said mixed C4 stream inlet is disposed above said first hydrogen inlet;
preferably, the height ratio of the selective hydrogenation catalyst bed to the selective hydrogenation zone is from 0.4 to 0.9:1, preferably 0.6 to 0.8: 1;
preferably, the bed of selective hydrogenation catalyst is disposed between the inlet of the mixed C4 stream and the first hydrogen inlet.
3. The apparatus of claim 1 or 2, wherein the total hydrogenation zone is further provided with a C4 alkane stream outlet and a second hydrogen inlet;
preferably, the C4 alkane stream outlet is disposed above the second hydrogen inlet;
preferably, the height ratio of the total hydrogenation catalyst bed layer to the total hydrogenation zone is 0.3-0.9: 1, preferably 0.6 to 0.8: 1;
preferably, the full hydrogenation zone catalyst bed is arranged between the outlet of the C4 alkane stream and the inlet of the second hydrogen.
4. The apparatus of any one of claims 1 to 3, wherein the ratio of the radii of the selective hydrogenation zone to the total hydrogenation zone is from 0.5 to 1.5: 1, preferably 0.8 to 1.2: 1;
preferably, the ratio of the height of the partition to the height of the divided wall column is from 0.5 to 0.9:1, preferably 0.7 to 0.9: 1.
5. a process for the total hydrogenation of a mixed C4 stream, comprising the steps of:
(1) in the presence of a selective hydrogenation catalyst, the mixed C4 material flow containing alkyne is in countercurrent contact with first hydrogen to carry out selective hydrogenation reaction, so that the alkyne is saturated into olefin, and a selective hydrogenation product is obtained; simultaneously, under the stripping action of first hydrogen, separating light components and heavy components from the selective hydrogenation product;
(2) said light components are mixed with unreacted first hydrogen and condensed, the resulting condensate is returned and mixed into said mixed C4 stream;
(3) contacting the mixture with a second hydrogen in the presence of a full hydrogenation catalyst to perform a full hydrogenation reaction to obtain a C4 alkane stream, wherein the mixture contains the heavy components and unreacted unsaturated hydrocarbons in the mixed C4 stream;
wherein the method is carried out in an apparatus according to any one of claims 1 to 4.
6. The process according to claim 5, wherein the alkyne content is from 20 to 50 wt%, preferably from 30 to 40 wt%, based on the weight of the mixed C4 stream;
preferably, the mixed C4 stream also contains olefins having a butene content of 5 to 30 wt%, preferably 5 to 15 wt%, based on the weight of the mixed C4 stream; the butadiene content is from 20 to 40% by weight, preferably from 20 to 30% by weight;
preferably, the mixed C4 stream is from a butadiene extraction unit and/or a hydrocarbon steam cracking unit.
7. The process according to claim 5 or 6, wherein the alkyne is selected from at least one of methylacetylene, ethylacetylene and vinylacetylene;
preferably, the molar ratio of the mixed C4 stream to the first hydrogen is 1: 0.5 to 3, preferably 1: 0.5-1.5;
preferably, the conditions of the selective hydrogenation reaction include: the pressure is 0.1-5MPa, preferably 0.6-4 MPa; the temperature is 20-80 ℃, and preferably 30-80 ℃; the volume space velocity is 10-100h-1Preferably 10-50h-1。
8. The process of any of claims 5-7, wherein the selective hydrogenation catalyst comprises a first active component and a first support;
preferably, the first active component comprises a first main active component and optionally a first co-active component;
preferably, the first main active component is present in an amount of from 0.01 to 1.5 wt%, preferably from 0.1 to 0.3 wt%, based on the weight of the selective hydrogenation catalyst; the content of the first auxiliary active component is 0-25 wt%, preferably 0-12 wt%;
preferably, the specific surface area of the first support is 1 to 250m2A/g, preferably from 80 to 200m2(ii)/g; the average pore diameter is 5-300nm, preferably 50-200 nm; the pore volume is 0.2-1mL/g, preferably 0.3-0.7 mL/g.
9. The method of any one of claims 5-8, wherein the molar ratio of the mixture to the second hydrogen is 1: 0.1 to 6; preferably 1: 0.4-4.5;
preferably, the conditions of the total hydrogenation reaction include: the pressure is 1-10MPa, preferably 1-4 MPa; the temperature is 10-80 ℃, and the preferred temperature is 20-50 ℃; the volume space velocity is 5-100h-1Preferably 10-40h-1。
10. The process of any of claims 5-9, wherein the total hydrogenation catalyst comprises a second active component and a second support;
preferably, the second active component comprises a second main active component and optionally a second co-active component;
preferably, the second main active component is present in an amount of 0.01 to 1 wt%, preferably 0.05 to 0.8 wt%, based on the weight of the perhydrogenation catalyst; the content of the second auxiliary active component is 0.001-1 wt%, preferably 0.05-0.8 wt%;
preferably, the specific surface area of the second carrier is 1 to 300m2Per g, preferably 100-2(ii)/g; the average pore diameter is 5-250nm, preferably 50-200 nm; the pore volume is 0.3-1.5mL/g, preferably 0.5-1.0 mL/g.
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Citations (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2130567A1 (en) * 1992-02-19 1993-09-02 Kinetics Technology International Corporation Absorption process for ethylene and hydrogen recovery
US20030181772A1 (en) * 2000-05-09 2003-09-25 Gerald Meyer Method and device for treating a c4 fraction
CN1453336A (en) * 2002-04-26 2003-11-05 中国石油化工股份有限公司 Catalytic distillation method for selective hydrogenation of C4 hydrocarbon mixture
US20030230516A1 (en) * 2001-10-16 2003-12-18 Johnson Kenneth H. Process for ultra low sulfur gasoline
US20040192994A1 (en) * 2003-03-26 2004-09-30 Bridges Robert S. Propylene production
CN1671638A (en) * 2002-07-24 2005-09-21 巴斯福股份公司 Continuous method for separating a c4 cut
US20060173224A1 (en) * 2005-02-01 2006-08-03 Catalytic Distillation Technologies Process and catalyst for selective hydrogenation of dienes and acetylenes
US20060183952A1 (en) * 2005-02-16 2006-08-17 Catalytic Distillation Technologies Process for the removal of benzene from gasoline streams
CN1872819A (en) * 2005-05-31 2006-12-06 中国石油化工股份有限公司 Counter flow typed selective method for adding hydrogen
US20080119675A1 (en) * 2004-04-09 2008-05-22 Institut Francais Du Petrole Process and Apparatus for Treating a Feed Comprising Butadiene
CN101423452A (en) * 2007-10-31 2009-05-06 中国石油化工股份有限公司 Selective hydrogenation method for foreshot high unsaturated hydrocarbons mixed phase
CN101613621A (en) * 2008-06-26 2009-12-30 中国石油化工股份有限公司 Splitting gas is selected hydrogenation and separation method
CN201834883U (en) * 2010-10-13 2011-05-18 中国石油化工股份有限公司 Hydrogenation processing reactor for acid-containing crude oil
CN102443435A (en) * 2010-10-13 2012-05-09 中国石油化工股份有限公司 Heavy oil hydrogenation method utilizing partition plate type reactor
CN103370397A (en) * 2010-06-30 2013-10-23 埃克森美孚研究工程公司 Two stage hydroprocessing with divided wall column fractionator
CN103787813A (en) * 2012-10-30 2014-05-14 中国石油化工股份有限公司 Butadiene tail gas hydrogenation device and method
CN104926584A (en) * 2014-03-19 2015-09-23 中国石化工程建设有限公司 System and method for preparing isobutane
CN105524656A (en) * 2015-11-26 2016-04-27 何巨堂 Hydrocarbon hydro-upgrading method using gas-stripped hydrogen to separate hydrogenation products
US20180170839A1 (en) * 2016-12-16 2018-06-21 Janus Technology Solutions, LLC Recovery of Hydrogen and Ethylene from Fluid Catalytic Cracking Refinery Off Gas
CN109022013A (en) * 2017-06-09 2018-12-18 何巨堂 Heat from hydrogenation cracking reaction process and combined type hydrogenator applied to the process
CN109929585A (en) * 2017-12-19 2019-06-25 何巨堂 Condense the hydrocarbon material process for selective hydrogenation of middle matter hydrocarbon in the gas phase of reuse reaction product
CN110819383A (en) * 2018-08-14 2020-02-21 何巨堂 Process for the upflow hydrogenation of poor quality hydrocarbons using reactors with internal parallel reaction zones

Patent Citations (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2130567A1 (en) * 1992-02-19 1993-09-02 Kinetics Technology International Corporation Absorption process for ethylene and hydrogen recovery
US20030181772A1 (en) * 2000-05-09 2003-09-25 Gerald Meyer Method and device for treating a c4 fraction
US20030230516A1 (en) * 2001-10-16 2003-12-18 Johnson Kenneth H. Process for ultra low sulfur gasoline
CN1453336A (en) * 2002-04-26 2003-11-05 中国石油化工股份有限公司 Catalytic distillation method for selective hydrogenation of C4 hydrocarbon mixture
CN1671638A (en) * 2002-07-24 2005-09-21 巴斯福股份公司 Continuous method for separating a c4 cut
US20060021911A1 (en) * 2002-07-24 2006-02-02 Till Adrian Continuous method for separating a c4 cut
US20040192994A1 (en) * 2003-03-26 2004-09-30 Bridges Robert S. Propylene production
US20080119675A1 (en) * 2004-04-09 2008-05-22 Institut Francais Du Petrole Process and Apparatus for Treating a Feed Comprising Butadiene
US20060173224A1 (en) * 2005-02-01 2006-08-03 Catalytic Distillation Technologies Process and catalyst for selective hydrogenation of dienes and acetylenes
US20060183952A1 (en) * 2005-02-16 2006-08-17 Catalytic Distillation Technologies Process for the removal of benzene from gasoline streams
CN1872819A (en) * 2005-05-31 2006-12-06 中国石油化工股份有限公司 Counter flow typed selective method for adding hydrogen
CN101423452A (en) * 2007-10-31 2009-05-06 中国石油化工股份有限公司 Selective hydrogenation method for foreshot high unsaturated hydrocarbons mixed phase
CN101613621A (en) * 2008-06-26 2009-12-30 中国石油化工股份有限公司 Splitting gas is selected hydrogenation and separation method
CN103370397A (en) * 2010-06-30 2013-10-23 埃克森美孚研究工程公司 Two stage hydroprocessing with divided wall column fractionator
CN102443435A (en) * 2010-10-13 2012-05-09 中国石油化工股份有限公司 Heavy oil hydrogenation method utilizing partition plate type reactor
CN201834883U (en) * 2010-10-13 2011-05-18 中国石油化工股份有限公司 Hydrogenation processing reactor for acid-containing crude oil
CN103787813A (en) * 2012-10-30 2014-05-14 中国石油化工股份有限公司 Butadiene tail gas hydrogenation device and method
CN104926584A (en) * 2014-03-19 2015-09-23 中国石化工程建设有限公司 System and method for preparing isobutane
CN105524656A (en) * 2015-11-26 2016-04-27 何巨堂 Hydrocarbon hydro-upgrading method using gas-stripped hydrogen to separate hydrogenation products
US20180170839A1 (en) * 2016-12-16 2018-06-21 Janus Technology Solutions, LLC Recovery of Hydrogen and Ethylene from Fluid Catalytic Cracking Refinery Off Gas
CN109022013A (en) * 2017-06-09 2018-12-18 何巨堂 Heat from hydrogenation cracking reaction process and combined type hydrogenator applied to the process
CN109929585A (en) * 2017-12-19 2019-06-25 何巨堂 Condense the hydrocarbon material process for selective hydrogenation of middle matter hydrocarbon in the gas phase of reuse reaction product
CN110819383A (en) * 2018-08-14 2020-02-21 何巨堂 Process for the upflow hydrogenation of poor quality hydrocarbons using reactors with internal parallel reaction zones

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