CN114471375B - Device and method for fully hydrogenating mixed C4 material flow - Google Patents

Device and method for fully hydrogenating mixed C4 material flow Download PDF

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CN114471375B
CN114471375B CN202011147995.6A CN202011147995A CN114471375B CN 114471375 B CN114471375 B CN 114471375B CN 202011147995 A CN202011147995 A CN 202011147995A CN 114471375 B CN114471375 B CN 114471375B
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selective hydrogenation
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hydrogen
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CN114471375A (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 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 the C4 alkane in the C4 alkane material.

Description

Device and method for fully hydrogenating mixed C4 material flow
Technical Field
The invention relates to the technical field of petrochemical industry, in particular to a device and a method for fully hydrogenating mixed C4 material flow.
Background
The ethylene preparation by hydrocarbon high-temperature steam cracking can produce a byproduct of mixed carbon four, wherein the cracked mixed carbon four contains a large amount of 1,3-butadiene, and a small amount of Vinyl Acetylene (VA) and Ethyl Acetylene (EA). In order to obtain 1,3-butadiene with high purity, which meets the requirements of polymer grade or higher, it is necessary to subject the C4 stream to alkyne removal. 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 separated alkyne contains 10-20wt% of 1,3-butadiene in addition to 20-40wt% 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 temperature in the reactor to rise rapidly. 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 can be further accelerated by the rising of the temperature of the reactor, so that the process has potential safety hazards and the service life of the catalyst is short.
CN101434508A discloses an alkyne selective hydrogenation method, which directly performs selective hydrogenation on alkyne-rich residue material after butadiene extraction, so that alkyne is converted into butadiene and mono-olefin, and a hydrogenation product can return 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 selectivity requirement on the catalyst.
CN1520387a discloses a selective acetylene hydrogenation process that can produce 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 polymer solvent, diene feed and hydrogen while the process unit remains in operation, and in a second experimental embodiment by contacting the selective hydrogenation catalyst while off-line with only polymer solvent and hydrogen. However, the method introduces a polymer solvent, and needs to perform corresponding subsequent removal operation, thereby having complex operation flow.
CN1872819A discloses a counter-flow selective hydrogenation method, wherein a mixed C4 hydrocarbon raw material and hydrogen respectively enter a tower from the upper part and the lower part of a counter-flow reactor through a distributor, a hydrocarbon fraction flowing downwards and hydrogen flowing upwards are in counter-flow 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 and flows out from the top of the reactor together with unreacted first hydrogen, and a refined mixed C4 product flows out from the bottom of the reactor. The mixed C4 hydrocarbon feedstock referred to in the 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 total hydrogenation, butadiene is caused to generate polymerization reaction, so that a catalyst is blocked and inactivated, the operation of a process flow is complex and the like, and provides a device and a method for the mixed C4 material flow total 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 carrying out countercurrent contact on a mixed C4 material flow containing alkyne and first hydrogen to saturate alkyne into olefin so as to 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 the condensate to be mixed 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 material flow, wherein the mixture contains the heavy component and unreacted unsaturated hydrocarbon in the mixed C4 material flow.
In a second aspect, the present invention provides a process for the total hydrogenation of a mixed C4 stream, said 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) Mixing the light components with unreacted first hydrogen and condensing to obtain condensate, and returning and mixing the condensate into the mixed C4 material flow;
(3) Contacting the mixture with a second hydrogen gas 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 component and unreacted unsaturated hydrocarbon in the mixed C4 alkane stream;
wherein the method is carried out in the apparatus provided in the first aspect.
Through the technical scheme, the device for fully hydrogenating the mixed C4 material flow, provided by the invention, adopts the separation wall tower which is provided with the external condensation and is divided into the selective hydrogenation area and the full hydrogenation area, the selective hydrogenation area and the full hydrogenation area are limited to be separated by the partition plate, the condenser is arranged outside the shell and positioned above the selective hydrogenation area, and the selective hydrogenation reaction, the material separation and the 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 for fully hydrogenating the mixed C4 material flow adopts a process of firstly carrying out selective hydrogenation and then carrying out full hydrogenation, namely acetylene hydrocarbon in the mixed C4 material flow is converted into butadiene and/or butylene before full hydrogenation, and the condensate is returned to the mixed C4 material flow to reduce the content of the acetylene hydrocarbon in the mixed C4 material flow, so that the heat release of the selective hydrogenation reaction is reduced, the service life of a selective hydrogenation catalyst is prolonged, and the content and the selectivity of C4 alkane are further improved by combining with the full hydrogenation reaction.
Drawings
FIG. 1 is a schematic diagram of a device for fully hydrogenating a mixed C4 material flow provided by the invention.
Description of the reference numerals
1. Mixing C4 material flow 2, first hydrogen 3 and selective hydrogenation catalyst bed layer
4. Tail gas 5, condensate 6 and partition board
7. Second hydrogen 8, full 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 vessel refers to 70-100% of the vessel 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 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 carrying out countercurrent contact on a mixed C4 material flow containing alkyne and first hydrogen to saturate alkyne into olefin so as to 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 the condensate to be mixed 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 material flow, wherein the mixture contains the heavy component and unreacted unsaturated hydrocarbon in the mixed C4 material flow.
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 invention, the selective hydrogenation products are butadiene and butylene, preferably, the butadiene is 1,3-butadiene and/or 1,2-butadiene, and the butylene is 1-butylene and/or 2-butylene; 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 the unreacted alkyne in the mixed C4 stream without special cases.
According to the present invention, preferably, the selective hydrogenation zone is provided with a mixed C4 stream inlet and a first hydrogen inlet.
In order to fully embody the countercurrent contact of the mixed C4 stream with the first hydrogen and to increase the saturation ratio 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 total 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 arranged 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 column is partitioned into a selective hydrogenation zone and a butadiene extraction zone.
An apparatus for the total hydrogenation of 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;
and the full hydrogenation zone IV is provided with a full hydrogenation catalyst bed layer 8 and is used for contacting a mixture with a second hydrogen gas 7 to perform a full hydrogenation reaction to obtain a C4 alkane material flow 9, wherein the mixture contains the heavy component and unreacted unsaturated hydrocarbon in the mixed C4 material flow.
Preferably, the selective hydrogenation zone III is further provided with the mixed C4 stream inlet and a first hydrogen inlet, and the selective hydrogenation catalyst bed 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) Mixing the light components with unreacted first hydrogen and condensing to obtain condensate, and returning and mixing the condensate into the mixed C4 material flow;
(3) Contacting the mixture with a second hydrogen gas 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 component and unreacted unsaturated hydrocarbon in the mixed C4 alkane 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 sudden rise of the bed temperature caused by the heat release of the selective hydrogenation reaction is favorably reduced by reducing the content of the acetylene hydrocarbon, the generation of a polymer and the deposition on the surface of the 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, preferably, the alkyne content is in the range of from 20 to 50wt%, preferably from 30 to 40wt%, 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 30wt%, preferably from 5 to 15wt%, 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 gas chromatography.
In the present invention, there is a wide choice of sources for the mixed C4 stream, as long as the alkyne content in the mixed C4 stream is in the range of from 20 to 50wt%. 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. Adopting the optimized conditions to be more favorable for completely converting the alkynes in the mixed C4 material flow into butadiene and butylene; wherein the butene is mainly 1-butene.
In the present invention, the conditions of the selective hydrogenation reaction have a wide range of selection, so long as the acetylene hydrocarbon in the mixed C4 material flow is subjected to the selective hydrogenation reaction to be converted into butadiene and butene. Preferably, the conditions of the selective hydrogenation reaction include: the pressure is 0.1-5MPa, preferably 0.6-4MPa; the temperature is 20-80 ℃, and preferably 30-80 ℃; the volume space velocity is 10-100h -1 Preferably 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, as long as the alkyne in the mixed C4 stream and the first hydrogen undergo the 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 1.5wt%, preferably 0.1 to 0.3wt%, based on the weight of the selective hydrogenation catalyst; the content of the first co-active component is 0-25wt%, preferably 0-12wt%.
According to the present invention, preferably, the first main active component is selected from at least one of palladium, rhodium, platinum and nickel, and is 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 250m 2 A ratio of/g, preferably 80 to 200m 2 (iv) g; the average pore diameter is 5-300nm, preferably 50-200nm; the pore volume is 0.2-1mL/g, preferably 0.3-0.7mL/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 for the mixed C4 stream is located above the inlet for 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 present invention, the condensate is returned and mixed into the mixed C4 stream, which facilitates to reduce the bed temperature shock caused by the heat release of the selective hydrogenation reaction by reducing the content of alkyne, effectively inhibits the generation of polymer and the deposition on the surface of the selective hydrogenation catalyst, and prolongs the service life of the selective hydrogenation catalyst.
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 selection of the conditions for 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 1-4MPa; the temperature is 10-80 ℃, and the preferred temperature is 20-50 ℃; the volume space velocity is 5-100h -1 Preferably 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 1wt%, preferably 0.05 to 0.8wt%, based on the weight of the total hydrogenation catalyst; the content of the second co-active component is 0.001 to 1wt%, preferably 0.05 to 0.8wt%.
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 300m 2 A/g, preferably from 100 to 200m 2 (ii)/g; the average pore diameter is 5-250nm, preferably 50-200nm; the pore volume is 0.3-1.5mL/g, preferably 0.5-1mL/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 feedstock to continue participating in the cracking reaction. By adopting the optimal mode, the utilization rate of the mixed C4 material flow is improved.
According to the present invention, preferably, the C4 alkane stream has a C4 alkane content of from 60 to 95wt%, preferably from 80 to 90wt%.
Preferably, the C4 alkane selectivity in 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) An 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 of the separation wall tower I and the tower wall 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;
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;
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 6 to the partition wall column I is 0.9.
(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 200m 2 And/g, the average pore diameter is 250nm, the pore volume is 0.8 mL/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 -1 To obtain selective hydrogenation products; simultaneously, under the steam stripping action of first hydrogen, separating light components and heavy components from the hydrogenation product;
b. mixing the light components with unreacted first hydrogen and condensing to obtain condensate, and returning and mixing the condensate 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 0.1wt%, the content of the silver is 0.2wt%, and the specific surface area of the alumina is 250m 2 Per g, average pore diameter of 150nm and pore volume of 1 mL/g), and carrying out full hydrogenation reaction on a mixture and a second hydrogen according to a molar ratio of 1: the pressure is 2.4MPa, the temperature is 35 ℃, and the volume space velocity is 30h -1 To obtain C4 alkane material flow S1.
Wherein, in the C4 alkane material flow S1, the content of the C4 alkane is 88wt%, and the selectivity of the C4 alkane is 84%.
Example 2
(1) An apparatus for the total hydrogenation of a mixed C4 stream is shown in FIG. 1, i.e., the apparatus comprises: a divided wall column I, saidThe 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 of the dividing wall tower I and the tower wall 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 the condenser II is provided with a condensate outlet 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;
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;
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 6 to the partition wall column I is 0.9.
(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 0.15wt%, the content of the lead is 10wt%, and the specific surface area of the alumina is 180m 2 And/g, the average pore diameter is 260nm, the pore volume is 1.5 mL/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 -1 To obtain selective hydrogenation products; at the same time, in the first hydrogenUnder the stripping action of (3), separating light components and heavy components from the hydrogenation product;
b. the light components are mixed with unreacted first hydrogen, the mixed product is 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 0.4wt%, the content of the silver is 0.3wt%, and the specific surface area of the alumina is 280m 2 Per g, average pore diameter of 200nm and pore volume of 0.7 mL/g), and a second hydrogen gas in a molar ratio of 1:3, wherein the mixture contains unreacted unsaturated hydrocarbons and heavy components in a mixed C4 stream, wherein the conditions of the total hydrogenation reaction include: the pressure is 3MPa, the temperature is 50 ℃, and the volume space velocity is 25h -1 To obtain C4 alkane material flow S2.
Wherein, in the C4 alkane material flow S2, the content of the C4 alkane is 80wt%, and the selectivity of the C4 alkane is 78%.
Example 3
(1) An 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 of the separation wall tower I and the tower wall 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;
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;
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 6 to the partition wall column I is 0.8.
(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 0.18wt%, the content of the lead is 12wt%, and the specific surface area of the alumina is 100m 2 A mixed C4 stream (hydrocarbon steam cracking unit, alkyne content 35 wt%) and a first hydrogen are subjected to a selective hydrogenation reaction according to a molar ratio of 1:1.5 in the presence of a mixed C4 stream (hydrocarbon steam cracking unit, alkyne content 35 wt%), wherein the conditions of the selective hydrogenation reaction comprise: the pressure is 3MPa, the temperature is 70 ℃, and the volume space velocity is 50h -1 To 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 product is 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 0.7wt%, the content of the silver is 0.6wt%, and the specific surface area of the alumina is 180m 2 Per g, average pore diameter of 170nm, pore volume of 0.5 mL/g), and a second hydrogen gas in a molar ratio of 1:4, wherein the mixture comprises unreacted unsaturated hydrocarbons and heavies in a mixed C4 stream, under conditions comprising: the pressure is 3.5MPa, the temperature is 48 ℃, and the volume space velocity is 50h -1 To obtain C4 alkane material flow S3.
Wherein, in the C4 alkane material flow S3, the content of the C4 alkane is 85wt%, and the selectivity of the C4 alkane is 80%.
Comparative example 1
The process of example 1 is followed, except that step b is omitted, yielding a C4 alkane stream D1.
Wherein, in the C4 alkane material flow D1, the content of the C4 alkane is 60wt%, and the selectivity of the C4 alkane is 48%.
Comparative example 2
The process of example 1 is followed except that in step b, no condensate is returned and mixed into the mixed C4 stream to provide C4 alkane stream D2.
Wherein, in the C4 alkane material flow D2, the content of the C4 alkane is 50wt%, and the selectivity of the C4 alkane is 36%.
Comparative example 3
According to the process of example 1, except that the apparatus for the total hydrogenation of a mixed C4 stream is different from the apparatus shown in fig. 1, it is carried out in a selective hydrogenation reactor and a total hydrogenation reactor, respectively, i.e. a divided wall column without a selective hydrogenation zone and a total hydrogenation zone, to obtain a C4 alkane stream D3.
Wherein, in the C4 alkane material flow D3, the content of the C4 alkane is 65wt%, 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 streams provided by the present invention, i.e., the divided wall column with an external condenser and divided into a selective hydrogenation zone and a total hydrogenation zone, simultaneously achieves selective hydrogenation reaction and total hydrogenation reaction of mixed C4 streams, simplifies the operation flow, reduces the retention time of the material, increases the content and yield of C4 alkanes in the mixed C4 streams, and also increases 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 various technical features being combined 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 (42)

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 carrying out a selective hydrogenation reaction by carrying out countercurrent contact on a mixed C4 material flow containing alkyne and first hydrogen to saturate alkyne into olefin so as to 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 the condensate to be mixed 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 a full hydrogenation reaction to obtain a C4 alkane material flow, wherein the mixture contains the heavy components and unreacted unsaturated hydrocarbons in the mixed C4 material flow.
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.
3. The apparatus of claim 2, wherein the mixed C4 stream inlet is disposed above the first hydrogen inlet.
4. The apparatus of claim 2, wherein the height ratio of the bed of selective hydrogenation catalyst to the selective hydrogenation zone is from 0.4 to 0.9:1.
5. the apparatus of claim 2, wherein the height ratio of the bed of selective hydrogenation catalyst to the selective hydrogenation zone is from 0.6 to 0.8:1.
6. the apparatus of claim 2, wherein the bed of selective hydrogenation catalyst is disposed between the mixed C4 stream inlet and the first hydrogen inlet.
7. The apparatus of any one of claims 1-6, wherein the total hydrogenation zone is further provided with a C4 alkane stream outlet and a second hydrogen inlet.
8. The apparatus of claim 7, wherein the C4 alkane stream outlet is disposed above the second hydrogen inlet.
9. The apparatus of claim 7, wherein the height ratio of the fully hydrogenated catalyst bed to the fully hydrogenated zone is from 0.3 to 0.9:1.
10. the apparatus of claim 7, wherein the height ratio of the fully hydrogenated catalyst bed to the fully hydrogenated zone is from 0.6 to 0.8:1.
11. the apparatus of claim 7, wherein the full hydrogenation zone catalyst bed is disposed between the C4 alkane stream outlet and the second hydrogen inlet.
12. The apparatus of any one of claims 1-6, wherein the ratio of the vertical distance of the side wall of the selective hydrogenation zone from the central axis of the partition to the vertical distance of the side wall of the total hydrogenation zone from the central axis of the partition is from 0.5 to 1.5:1.
13. the apparatus of claim 12, wherein the ratio of the vertical distance of the side wall of the selective hydrogenation zone from the central axis of the partition to the vertical distance of the side wall of the total hydrogenation zone from the central axis of the partition is from 0.8 to 1.2:1.
14. the apparatus of claim 12, wherein the ratio of the height of the partition to the divided wall column is from 0.5 to 0.9:1.
15. the apparatus of claim 12, wherein the ratio of the height of the partition to the divided wall column is from 0.7 to 0.9:1.
16. a process for the total hydrogenation of a mixed C4 stream, characterized in that the process comprises 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) Mixing the light components with unreacted first hydrogen and condensing to obtain condensate, and returning and mixing the condensate into the mixed C4 material flow;
(3) Contacting the mixture with a second hydrogen gas 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 component and unreacted unsaturated hydrocarbon in the mixed C4 alkane stream;
wherein the method is carried out in an apparatus according to any one of claims 1 to 15.
17. The process of claim 16, wherein the alkyne is present in an amount of 20 to 50wt% based on the weight of the mixed C4 stream.
18. The process according to claim 17, wherein the alkyne is present in an amount of from 30 to 40 wt.% based on the weight of the mixed C4 stream.
19. The process of claim 17 wherein said mixed C4 stream further comprises olefins, wherein said olefins have a butene content of from 5 to 30wt%, based on the weight of said mixed C4 stream; the butadiene content is 20 to 40 wt.%.
20. The process of claim 17 wherein said mixed C4 stream further comprises olefins, wherein said olefins have a butene content of from 5 to 15wt%, based on the weight of said mixed C4 stream; the butadiene content is 20 to 30 wt.%.
21. The process of claim 17, wherein the mixed C4 stream is from a butadiene extraction unit and/or a hydrocarbon steam cracking unit.
22. The method according to any one of claims 16-21, wherein the alkyne is selected from at least one of methylacetylene, ethylacetylene and vinylacetylene.
23. The method of claim 22, wherein the molar ratio of the mixed C4 stream to the first hydrogen is from 1:0.5-3.
24. The method of claim 22, wherein the molar ratio of the mixed C4 stream to the first hydrogen is from 1:0.5-1.5.
25. The method of claim 22, wherein the conditions of the selective hydrogenation reaction comprise: the pressure is 0.1-5MPa; the temperature is 20-80 ℃; the volume space velocity is 10-100h -1 。
26. The method of claim 22, wherein the conditions of the selective hydrogenation reaction comprise: the pressure is 0.6-4MPa; the temperature is 30-80 ℃; the volume space velocity is 10-50h -1 。
27. The process of any of claims 16-21, wherein the selective hydrogenation catalyst comprises a first active component and a first support.
28. The method of claim 27, wherein the first active component comprises a first primary active component and a first co-active component.
29. The process of claim 28, wherein the first primary active component is present in an amount of from 0.01 to 1.5wt%, based on the weight of the selective hydrogenation catalyst; the content of the first auxiliary active component is 0-25wt%.
30. The process of claim 28, wherein the first primary active component is present in an amount of from 0.1 to 0.3wt%, based on the weight of the selective hydrogenation catalyst; the content of the first auxiliary active component is 0-12wt%.
31. The method of claim 27, wherein the first support has a specific surface area of 1-250m 2 (ii)/g; the average pore diameter is 5-300nm; the pore volume is 0.2-1mL/g.
32. The method of claim 27, wherein the first support has a specific surface area of 80-200m 2 (ii)/g; the average pore diameter is 50-200nm; the pore volume is 0.3-0.7mL/g.
33. The method of any one of claims 16-21, wherein the molar ratio of the mixture to the second hydrogen is 1:0.1-6.
34. The method of claim 33, wherein the molar ratio of the mixture to the second hydrogen is 1:0.4-4.5.
35. The method of claim 33, wherein the first and second light sources are selected from the group consisting of,wherein the conditions of the full hydrogenation reaction comprise: the pressure is 1-10MPa; the temperature is 10-80 ℃; the volume space velocity is 5-100h -1 。
36. The process of claim 33, wherein the conditions of the total hydrogenation reaction comprise: the pressure is 1-4MPa; the temperature is 20-50 ℃; the volume space velocity is 10-40h -1 。
37. The process of any of claims 16-21, wherein the total hydrogenation catalyst comprises a second active component and a second support.
38. The method of claim 37, wherein the second active component comprises a second primary active component and a second co-active component.
39. The process of claim 38, wherein the second primary active component is present in an amount of from 0.01 to 1wt%, based on the weight of the total hydrogenation catalyst; the content of the second auxiliary active component is 0.001-1wt%.
40. The process of claim 38, wherein the second primary active component is present in an amount of from 0.05 to 0.8wt%, based on the weight of the total hydrogenation catalyst; the content of the second auxiliary active component is 0.05-0.8wt%.
41. The method of claim 37, wherein the second support has a specific surface area of 1-300m 2 (ii)/g; the average pore diameter is 5-250nm; the pore volume is 0.3-1.5mL/g.
42. The method of claim 37, wherein the second support has a specific surface area of 100-200m 2 (ii)/g; the average pore diameter is 50-200nm; the pore volume is 0.5-1.0mL/g.
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