CN114763495A

CN114763495A - Catalytic conversion method for preparing ethylene, propylene and butylene

Info

Publication number: CN114763495A
Application number: CN202110031551.4A
Authority: CN
Inventors: 许友好; 左严芬; 王新; 何鸣元; 沙有鑫; 白旭辉
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2021-01-11
Filing date: 2021-01-11
Publication date: 2022-07-19
Anticipated expiration: 2041-01-11
Also published as: CN114763495B

Abstract

The present disclosure relates to a catalytic conversion process for producing ethylene, propylene and butylene. The method comprises the steps of carrying out catalytic cracking on a raw material rich in olefin in a first reaction zone of a catalytic conversion reactor, then contacting a mixed material flow in the first reaction zone with a heavy raw material in a second reaction zone for catalytic cracking reaction, then carrying out first separation treatment and second separation treatment on a reaction product, enabling the obtained material flow rich in olefin to be used for catalytic cracking again, and further carrying out production of ethylene, propylene and butylene by utilizing a material containing oil olefin in the reaction product per se, so that the utilization rate of petrochemical resources is improved; the heavy raw material is introduced into the production process, so that the heavy oil is recycled, and the cost is reduced; the catalytic conversion method for preparing the ethylene, the propylene and the butylene has higher yield and selectivity of the ethylene, the propylene and the butylene, can reduce the generation of hydrogen, methane and ethane, and particularly can inhibit the generation of methane.

Description

Catalytic conversion method for preparing ethylene, propylene and butylene

Technical Field

The application relates to petroleum refining and petrochemical processing processes, in particular to a catalytic conversion method for preparing ethylene, propylene and butylene.

Background

Olefins of four carbon atoms and below are important chemical raw materials, and typical products include: ethylene, propylene and butylene. On the one hand, with the continuous and accelerated development of economy, the demand of various industries for light oil products and clean fuel oil is also rapidly increased. On the other hand, with the increasing of the oil field exploitation amount, the available yield of conventional crude oil is gradually reduced, the quality of crude oil is gradually poor and tends to be deteriorated and heavy, and although the production capacity of light olefins in China is rapidly increased, the demand of the domestic market for the light olefins cannot be met at present.

The main products produced by ethylene include polyethylene, ethylene oxide, ethylene glycol, polyvinyl chloride, styrene, vinyl acetate and the like. The main products produced by adopting propylene comprise acrylonitrile, propylene oxide, acetone and the like; the main products produced by using butylene comprise butadiene, and are used for manufacturing methyl ethyl ketone, sec-butyl alcohol, butylene oxide and butylene polymers and copolymers, and the main products produced by using isobutylene comprise butyl rubber, polyisobutylene rubber and various plastics. Therefore, there is an increasing demand for ethylene, propylene and butylene for the production of various important organic chemicals, the production of synthetic resins, synthetic rubbers and various fine chemicals, etc.

The traditional route of preparing ethylene and propylene by steam cracking is adopted, the demand for chemical light hydrocarbons such as light hydrocarbons and naphtha is large, 70 ten thousand tons of chemical light oil is expected to be needed in 2025 years, while domestic crude oil is generally heavier, the chemical light oil cannot meet the demand of generating ethylene, propylene and butylene raw materials easily, and under the condition of insufficient petroleum resources, the diversification of the steam cracking raw materials becomes the industrial development trend of the ethylene and the propylene. The steam cracking raw materials mainly comprise light hydrocarbons (such as ethane, propane and butane), naphtha, diesel oil, condensate oil and hydrogenated tail oil, wherein the mass fraction of the naphtha accounts for more than 50%, the ethylene yield of typical naphtha steam cracking is about 29-34%, the propylene yield is 13-16%, and the lower ethylene-propylene yield ratio is difficult to meet the current situation of the current low-carbon olefin demand.

CN101092323A discloses a method for preparing ethylene and propylene by using a C4-C8 olefin mixture as a raw material, reacting at the reaction temperature of 400-600 ℃ and the absolute pressure of 0.3-1.1KPa, and recycling 30-90 wt% of a C4 fraction into a reactor through a separation device for cracking again. The method focuses on circulation of C4 fraction, improves the conversion rate of olefin, obtains ethylene and propylene which are not less than 62% of the total amount of the raw material olefin, but has small ethylene/propylene ratio, can not be flexibly adjusted according to market demands, and has low reaction selectivity.

CN101239878A discloses that an olefin-rich mixture of four or more carbon olefins is used as a raw material, the reaction is carried out at a reaction temperature of 400-680 ℃, a reaction pressure of-0.09-1.0 MPa and a weight space velocity of 0.1-50 h < -1 >, the product ethylene/propylene is lower and lower than 0.41, the ethylene/propylene is increased along with the temperature rise, and simultaneously hydrogen, methane and ethane are increased.

Disclosure of Invention

The invention aims to provide a catalytic conversion method for preparing ethylene, propylene and butylene, and the processing method provided by the disclosure can obviously improve the yield and selectivity of the ethylene, the propylene and the butylene.

In order to achieve the above objects, the present disclosure provides a catalytic conversion process for producing ethylene, propylene and butylene, the process comprising the steps of:

(1) contacting an olefin-rich feedstock with a catalytic conversion catalyst at a temperature above 650 ℃ in a first reaction zone of a catalytic conversion reactor under first catalytic conversion reaction conditions, the olefin-rich feedstock containing greater than 50 wt% olefins;

(2) under the second catalytic conversion reaction condition, the heavy raw material is in contact reaction with the material flow from the first reaction zone in the second reaction zone of the catalytic conversion reactor to obtain reaction oil gas and a spent catalyst;

(3) carrying out first separation treatment on the reaction oil gas to separate ethylene, propylene, butylene, first catalytic cracking distillate oil and second catalytic cracking distillate oil; the initial boiling point of the first catalytic cracking distillate oil is any temperature between more than 20 ℃ and less than 140 ℃, the final boiling point of the second catalytic cracking distillate oil is any temperature between less than 550 ℃ and more than 250 ℃, and the cutting point between the first catalytic cracking distillate oil and the second catalytic cracking distillate oil is any temperature between 140 ℃ and 250 ℃;

subjecting the first catalytic cracking distillate oil to a second separation treatment to separate an olefin-rich stream containing 50 wt% or more of C5 and above olefins;

(4) returning said olefin-rich stream to said catalytic conversion reactor for continued reaction.

Optionally, the method further comprises: under the condition of hydrogenation reaction, the second catalytic cracking distillate oil is in contact reaction with a hydrogenation catalyst to obtain hydrogenated second catalytic cracking distillate oil, and the hydrogenated second catalytic cracking distillate oil returns to the catalytic conversion reactor for continuous reaction.

Optionally, the hydrogenated second catalytically cracked distillate oil returns to the second reaction zone of the catalytic conversion reactor for continuous reaction, and the stream rich in olefin returns to the first reaction zone of the catalytic conversion reactor for continuous reaction; wherein the first reaction zone is upstream of the second reaction zone in the direction of reaction feed flow.

Optionally, the separation system comprises a product fractionation unit and an olefin separation unit, the process comprising:

feeding the reaction oil gas into the product fractionating device to separate ethylene, propylene, butylene, the first catalytic cracking distillate oil and the second catalytic cracking distillate oil;

passing said first catalytically cracked distillate to said olefin separation unit to separate a first olefin containing stream and a second olefin containing stream; the cut point between the first olefin containing stream and the second olefin containing stream is any temperature between 140 ℃ and 200 ℃;

returning the first olefin-containing stream to the first reaction zone of the catalytic conversion reactor for further reaction, and returning the second olefin-containing stream to the third reaction zone of the catalytic conversion reactor for further reaction;

wherein the third reaction zone is located downstream of the second reaction zone in the direction of reaction feed flow.

Optionally, wherein the catalytic conversion reactor is a riser reactor, preferably a variable diameter riser reactor.

Optionally, the first catalytic conversion reaction conditions comprise:

the reaction temperature is 650-750 ℃, preferably 630-750 ℃ and more preferably 630-720 ℃;

the reaction pressure is 0.05-1MPa, preferably 0.1-0.8MPa, more preferably 0.2-0.5 MPa;

the reaction time is 0.01 to 100 seconds, preferably 0.1 to 80 seconds, more preferably 0.2 to 70 seconds;

the weight ratio of the catalytic conversion catalyst to the olefin-rich feedstock is (1-100): 1, preferably (3-150): 1, more preferably (4-120): 1;

the second catalytic conversion reaction conditions include:

the reaction temperature is 400-650 ℃, preferably 450-600 ℃, and more preferably 480-580 ℃;

the weight ratio of the catalytic conversion catalyst to the heavy raw material is (1-100): 1, preferably (3-70): 1, more preferably (4-30): 1.

optionally, the hydrogenation reaction conditions comprise: the hydrogen partial pressure is 3.0-20.0 MPa, the reaction temperature is 300-450 ℃, the hydrogen-oil volume ratio is 300-2000, and the volume space velocity is 0.1-3.0 hours^-1。

Optionally, the method further comprises: the spent catalyst is subjected to coke burning regeneration to obtain a regenerated catalyst; returning the regenerated catalyst to the first reaction zone of the catalytic conversion reactor as the catalytic conversion catalyst.

Optionally, the olefin content of the olefin-rich feedstock is 80 wt% or more, preferably 90 wt% or more, more preferably a pure olefin feedstock; the olefins in the olefin-rich feedstock are selected from olefins having 5 or more carbon atoms;

the heavy oil is selected from petroleum hydrocarbon and/or mineral oil; the petroleum hydrocarbon is one or more selected from vacuum gas oil, atmospheric gas oil, coking gas oil, deasphalted oil, vacuum residue, atmospheric residue and heavy aromatic raffinate oil; the mineral oil is selected from one or more of coal liquefied oil, oil sand oil and shale oil.

Optionally, the olefin-rich feedstock is derived from at least one of a cut fraction of more than five carbons produced by an alkane dehydrogenation unit, a cut fraction of more than five carbons produced by a catalytic cracking unit in an oil refinery, a cut fraction of more than five carbons produced by a steam cracking unit in an ethylene plant, an olefin-rich cut fraction of more than five carbons produced by an MTO byproduct, and an olefin-rich cut fraction of more than five carbons produced by an MTP byproduct;

optionally, the paraffinic feedstock of the paraffinic dehydrogenation unit is derived from at least one of naphtha, aromatic raffinate, and other light hydrocarbons.

Optionally, the catalytic conversion catalyst comprises from 1 to 50 wt% of a molecular sieve, from 5 to 99 wt% of an inorganic oxide, and from 0 to 70 wt% of a clay, based on the total weight of the catalytic conversion catalyst;

the molecular sieve comprises one or more of a large-pore molecular sieve, a medium-pore molecular sieve and a small-pore molecular sieve;

the catalytic conversion catalyst further comprises 0.1-3 wt% of metal ions based on the total weight of the catalytic conversion catalyst, wherein the metal ions are selected from one or more of VIII group metals, IVA group metals and rare earth metals.

Optionally, the hydrogenation catalyst comprises 20-90 wt% of a carrier, 10-80 wt% of a supported metal, and 0-10 wt% of an additive, based on the total weight of the hydrogenation catalyst;

the carrier is alumina and/or amorphous silicon-aluminum, the additive is selected from at least one of fluorine, phosphorus, titanium and platinum, and the load metal is VIB group metal and/or VIII group metal;

preferably, the group VIB metal is Mo or/and W, and the group VIII metal is Co or/and Ni.

Optionally, the olefin-rich stream comprises more than 50 wt% olefins, preferably more than 80 wt% olefins.

According to the technical scheme, the catalytic conversion method for preparing the ethylene, the propylene and the butylene is characterized in that the olefin-rich raw material is subjected to catalytic cracking in the first reaction zone of the catalytic conversion reactor, then the mixed material flow in the first reaction zone is contacted with the heavy raw material in the second reaction zone for catalytic cracking reaction, then the reaction product is subjected to first separation treatment and second separation treatment, the obtained olefin-rich material flow can be used for catalytic cracking again, and the material containing the oil olefin in the reaction product is used for further preparing the ethylene, the propylene and the butylene, so that the utilization rate of petrochemical resources is improved; the heavy raw material is introduced into the production process, so that the heavy oil is recycled, and the cost is reduced; the catalytic conversion method for preparing the ethylene, the propylene and the butylene has higher yield and selectivity of the ethylene, the propylene and the butylene, can reduce the generation of hydrogen, methane and ethane, and particularly can inhibit the generation of methane; the yields of benzene, toluene and xylene are also improved.

Additional features and advantages of the disclosure will be set forth in the detailed description which follows.

Drawings

The accompanying drawings, which are included to provide a further understanding of the disclosure and are incorporated in and constitute a part of this specification, illustrate embodiments of the disclosure and together with the description serve to explain the disclosure, but do not constitute a limitation of the disclosure. In the drawings:

FIG. 1 is a schematic flow diagram of a catalytic conversion process for producing ethylene, propylene and butylene according to a first embodiment of the present disclosure;

FIG. 2 is a schematic flow diagram of a catalytic conversion process for producing ethylene, propylene and butylene according to a second embodiment of the present disclosure.

Reference signs

I a first reaction zone II a second reaction zone III a third reaction zone

1 line 2 reactor 3 line

4 line 5 line 6 line

7 outlet section 8 settler 9 gas collection chamber

10 stripping section 11 pipeline 12 inclined tube

13 regenerator 14 hydrotreating reactor 15 line

16 line 17 line 18 line

19 large oil-gas pipeline 20 product separation device 21 pipeline

22 line 23 line 24 line

25 line 26 line 27 line

28 olefin separation unit 29 line 30 line

31 line 32 line

Detailed Description

The following describes in detail specific embodiments of the present disclosure. It should be understood that the detailed description and specific examples, while indicating the present disclosure, are given by way of illustration and explanation only, not limitation.

The present disclosure provides a catalytic conversion process for producing ethylene, propylene and butylene, comprising the steps of:

subjecting the first catalytically cracked distillate to a second separation process to separate an olefin-rich stream containing greater than 50 wt% of olefins having a carbon number of 5 and greater;

According to the catalytic conversion method for preparing the ethylene, the propylene and the butylene, the raw material rich in olefin is subjected to catalytic cracking in the first reaction zone of the catalytic conversion reactor, the mixed material flow in the first reaction zone is contacted with the heavy raw material in the second reaction zone for catalytic cracking reaction, then the reaction product is subjected to first separation treatment and second separation treatment, the obtained material flow rich in olefin can be used for catalytic cracking again, and the material containing the oil olefin in the reaction product is utilized for further preparing the ethylene, the propylene and the butylene, so that the utilization rate of petrochemical resources is improved; the heavy raw material is introduced into the production process, so that the heavy oil is recycled, and the cost is reduced; the catalytic conversion method for preparing the ethylene, the propylene and the butylene has higher yield and selectivity of the ethylene, the propylene and the butylene, can reduce the generation of hydrogen, methane and ethane, and particularly can inhibit the generation of methane; the yields of benzene, toluene and xylene are also improved.

The present inventors, after conducting a large number of alkane and alkene catalytic cracking experiments, surprisingly found that the yields and selectivities of ethylene, propylene and butene produced by olefin cracking are significantly superior to those of alkane by using alkene and alkane to react under the same catalytic cracking reaction conditions, respectively; and the product distribution difference of olefin and alkane catalytic cracking is obvious.

In one embodiment, the olefin-rich feedstock employed in the present disclosure has an olefin content of 80 wt.% or greater, preferably 90 wt.% or greater, more preferably a pure olefin feedstock; the olefins in the olefin-rich feedstock are selected from olefins having 5 or more carbon atoms. The inventor finds in research that the improvement of the content of the olefin in the raw material rich in the olefin is beneficial to the improvement of the yield and selectivity of the ethylene, the propylene and the butylene in the product, and the effect of adopting the olefin with the carbon number of 5 and above is more excellent.

In the present disclosure, in one embodiment, the olefin-rich feedstock may be derived from only an olefin-containing stream containing five or more olefins separated from the catalytic conversion product of the heavy oil feedstock, i.e., the olefin-rich feedstock is the olefins recycled in the system; in another embodiment, the olefin-rich feedstock can comprise an additional olefin feedstock in addition to the olefin-containing stream comprising carbon five and greater olefins described above, with no particular requirement for the amount of additional olefin feedstock.

In some embodiments of the present disclosure, the olefin-rich feedstock may be derived from any one or more of the following sources: at least one of a fraction containing more than five carbons produced by the alkane dehydrogenation device, a fraction containing more than five carbons produced by the catalytic cracking device in an oil refinery, a fraction containing more than five carbons produced by the steam cracking device in an ethylene plant, and an olefin-rich fraction containing more than five carbons as by-products such as MTO (methanol to olefin) and MTP (methanol to propylene). In further embodiments, the paraffinic feedstock employed in the dehydrogenation of alkanes to produce an olefin-rich feedstock may be derived from at least one of naphtha, aromatic raffinate, and/or other light hydrocarbons. In actual production, other different petrochemical plants can be adopted to produce the obtained alkane product.

In one embodiment, the alkane dehydrogenation process can be carried out using the following method: under the dehydrogenation reaction conditions, the alkane and the dehydrogenation catalyst are subjected to contact reaction in a dehydrogenation treatment reactor to obtain a raw material rich in olefin.

Wherein, the dehydrogenation reaction conditions comprise: the inlet temperature of the dehydrogenation reactor is 400-700 ℃, and the volume space velocity of alkane is 500-5000h^-1The pressure of the contact reaction is 0.04-1.1 bar.

The dehydrogenation catalyst consists of a carrier, and an active component and an auxiliary agent which are loaded on the carrier; optionally, the carrier is present in an amount of 60 to 90 wt%, the active component is present in an amount of 8 to 35 wt%, and the promoter is present in an amount of 0.1 to 5 wt%, based on the total weight of the dehydrogenation catalyst;

optionally, the support is alumina containing a modifier; wherein, based on the total weight of the dehydrogenation catalyst, the content of the modifier is 0.1-2 wt%, wherein the modifier can be La and/or Ce;

optionally, the active component is chromium; alternatively, the adjuvant may be a combination of bismuth and an alkali metal or a combination of bismuth and an alkaline earth metal component; wherein the molar ratio of bismuth to the active component is 1 (5-50); the molar ratio of bismuth to alkali metal components is 1: (0.1-5); the molar ratio of bismuth to alkaline earth metal component is 1: (0.1-5); the alkali metal component may be selected from one or more of Li, Na and K; the alkaline earth metal component may be selected from one or more of Mg, Ca and Ba.

In a preferred embodiment, the heavy oil employed in the present disclosure is selected from petroleum hydrocarbons and/or mineral oils; the petroleum hydrocarbon is one or more selected from vacuum gas oil, atmospheric gas oil, coking gas oil, deasphalted oil, vacuum residue, atmospheric residue and heavy aromatic raffinate oil; the mineral oil is selected from one or more of coal liquefied oil, oil sand oil and shale oil.

In one embodiment, the catalytic conversion reactor employed in the present disclosure may be selected from one or a combination of two of a riser, which may be a constant diameter riser reactor or a variable diameter fluidized bed reactor, a constant linear velocity fluidized bed, a constant diameter fluidized bed, an upflow conveyor line and a downflow conveyor line in series, and a fluidized bed reactor, which may be a constant linear velocity fluidized bed or a constant diameter fluidized bed.

In a preferred embodiment, the present disclosure employs a riser reactor as the catalytic conversion reactor; in a more preferred embodiment, the catalytic conversion reactor is a variable diameter riser reactor.

In one embodiment, the catalytic conversion process provided by the present disclosure to produce ethylene, propylene, and butylene can further comprise: under the condition of hydrogenation reaction, the second catalytic cracking distillate oil is in contact reaction with a hydrogenation catalyst to obtain hydrogenated second catalytic cracking distillate oil, and the hydrogenated second catalytic cracking distillate oil is returned to the catalytic conversion reactor for continuous reaction. In the embodiment, the reaction product catalytic wax oil is subjected to hydrotreating and then is introduced into the catalytic conversion reactor for continuous reaction, so that the utilization rate of raw materials is improved, and the yields of ethylene, propylene and butylene are increased.

In one embodiment, the reaction conditions for the contact reaction of the second catalytically cracked distillate and the hydrogenation catalyst may be: the hydrogen partial pressure is 3.0-20.0 MPa, the reaction temperature is 300-450 ℃, the hydrogen-oil volume ratio is 300-2000, and the volume space velocity is 0.1-3.0 hours^-1。

In one embodiment, during processing of a feedstock to produce ethylene, propylene, and butenes, the hydrogenated second catalytically cracked distillate is returned to the second reaction zone of the catalytic conversion reactor for continued reaction, and the olefin-rich stream is returned to the first reaction zone of the catalytic conversion reactor for continued reaction; wherein the first reaction zone is upstream of the second reaction zone in the direction of reaction feed flow. Specifically, referring to FIG. 1, a first reaction zone I is disposed upstream of a second reaction zone II in the direction of feed flow. In this embodiment, the high-temperature catalytic conversion catalyst firstly contacts and reacts with the first catalytic cracking distillate oil returned to the reactor, and then contacts and reacts with the hydrogenated second catalytic cracking distillate oil, so that the saturated hydrocarbon with larger carbon number contained in the second catalytic cracking distillate oil is firstly cracked into olefins of C5-C9 under relatively mild reaction conditions, and then returns to the reactor to be subjected to high-temperature cracking again, thereby further improving the ethylene yield.

In one embodiment, as shown in FIG. 2, the first reaction zone may be suitably expanded as appropriate for the case where the olefin-rich feedstock is available from the outside.

In a preferred embodiment, the separation system comprises a product fractionation unit and an olefin separation unit. The method provided by the present disclosure comprises:

feeding the reaction oil gas into the product fractionating device, and separating out ethylene, propylene, butylene, the first catalytic cracking distillate oil and the second catalytic cracking distillate oil;

passing said first catalytically cracked distillate to said olefin separation unit to separate a first olefin containing stream and a second olefin containing stream; the cut point between the first olefin containing stream and the second olefin containing stream is any temperature between 140 ℃ and 200 ℃; wherein the first olefin containing stream is a light fraction and the second olefin containing stream is a heavy fraction;

wherein the third reaction zone is downstream of the second reaction zone in the direction of reaction feed flow.

Specifically, in the embodiment where the catalytic conversion reactor is a riser reactor, the first reaction zone, the second reaction zone, and the third reaction zone are sequentially disposed from bottom to top.

In this embodiment, further, the first olefin-containing stream contains greater than 50 wt%, preferably greater than 80 wt%, of the olefins, and the second olefin-containing stream contains greater than 50 wt%, preferably greater than 80 wt%, of the olefins.

Specifically, referring to fig. 2, the first catalytically cracked distillate oil obtained by separating the reaction oil gas in the product fractionating apparatus 20 is fed to the olefin separating apparatus 28 via the line 26, the first olefin-containing stream obtained by separation is returned to the first reaction zone via the line 30, and the second olefin-containing stream is returned to the third reaction zone via the line 31.

In one embodiment, the reaction conditions of the third reaction zone include: the reaction temperature is 400-650 ℃, the reaction pressure is 0.05-1MPa, the reaction time is 0.01-100 seconds, and the weight ratio of the catalytic conversion catalyst to the second olefin-containing material flow is (1-100): 1.

the inventor finds out through a large number of experiments that: long carbon alkenes produce ethylene while suppressing methane formation are not as capable as short chain alkenes. By taking ethylene as an example for explanation, the longer the carbon chain of the olefin raw material subjected to catalytic cracking is, in order to avoid increasing by-products such as methane in the product due to the fact that the long carbon chain is cracked into small molecules at one time, the long carbon chain olefin can be cracked in a third reaction zone with relatively mild conditions to obtain the short carbon chain olefin of C5-C9, and then the short carbon chain olefin is returned to the device for cracking again, which is beneficial to improving the yield of ethylene and reducing the yield of methane. In the preferred embodiment, the olefin-containing material flows with different distillation ranges are respectively introduced into different reaction zones, so that the olefins with longer carbon chains can be prevented from being cracked into small molecules at one time, the yields of ethylene, propylene and butylene can be improved, and particularly the yield of ethylene can be improved.

In one embodiment, the present disclosure provides a catalytic conversion process for producing ethylene, propylene, and butylene wherein the first catalytic conversion reaction conditions comprise:

the weight ratio of the catalytic conversion catalyst to the olefin-rich feedstock is (1-100): 1, preferably (3-150): 1, more preferably (4-120): 1.

in one embodiment, the present disclosure provides a catalytic conversion process for producing ethylene, propylene, and butylene wherein the second catalytic conversion reaction conditions comprise:

the reaction pressure is 0.05 to 1MPa, preferably 0.1 to 0.8MPa, and more preferably 0.2 to 0.5 MPa;

in a preferred embodiment, the present disclosure can also subject the spent catalyst to coke-burning regeneration to obtain a regenerated catalyst; the regenerated catalyst is returned to the first reaction zone of the catalytic conversion reactor as the catalytic conversion catalyst, so that the recycling of the catalytic conversion catalyst is realized.

In one embodiment, the catalytic conversion catalyst comprises from 1 to 50 weight percent molecular sieve, from 5 to 99 weight percent inorganic oxide, and from 0 to 70 weight percent clay, based on the total weight of the catalytic conversion catalyst.

The molecular sieve is used as an active component of the catalytic conversion catalyst and can be selected from one or more of large-pore molecular sieves, medium-pore molecular sieves and small-pore molecular sieves.

In one embodiment, the medium pore molecular sieve may be a ZSM molecular sieve, and further, the ZSM molecular sieve may be one or more selected from ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38, and ZSM-48.

In one embodiment, the small pore molecular sieve may be a SAPO molecular sieve, and further, the SAPO molecular sieve may be selected from one or more of SAPO-34, SAPO-11, SAPO-47, and SSZ-13. In a further embodiment, the medium pore molecular sieve comprises from 50 wt% to 100 wt%, preferably from 70 wt% to 100 wt%, and the small pore molecular sieve comprises from 0 wt% to 50 wt%, preferably from 0 wt% to 30 wt%, of the total weight of the molecular sieve.

In one embodiment, the large pore molecular sieve may be selected from one or a mixture of more than one of rare earth Y molecular sieves, rare earth hydrogen Y molecular sieves, ultrastable Y molecular sieves, high silicon Y molecular sieves, Beta molecular sieves, and other molecular sieves of similar structure.

In a preferred embodiment, the molecular sieve may also be loaded with metal ions, the metal ions may be selected from one or more of group VIII metals, group IVA metals, and rare earth metals; in a more preferred embodiment, the supported metal ion content by weight is 0.1% to 3% based on the total weight of the catalytic conversion catalyst, which can further improve the catalytic ability of the catalytic conversion catalyst.

In a preferred embodiment, the inorganic oxide is selected from the group consisting of silicon dioxide (SiO) as a binder₂) And/or aluminum oxide (Al)₂O₃) (ii) a The clay is selected from kaolin and/or halloysite as a matrix (i.e., carrier).

In one embodiment, the hydrogenation catalyst comprises a carrier and a metal component and an optional additive, wherein the metal component and the optional additive are loaded on the carrier, the carrier is alumina and/or amorphous silicon-aluminum, the metal component is a group VIB metal and/or a group VIII metal, the additive is at least one selected from fluorine, phosphorus, titanium and platinum, the group VIB metal is Mo or/and W, and the group VIII metal is Co or/and Ni; based on the total weight of the hydrogenation catalyst, the additive accounts for 0-10 wt%, the VIB group metal accounts for 12-39 wt%, and the VIII group metal accounts for 1-9 wt%.

In one embodiment, the olefin-rich stream returned to the catalytic conversion reactor contains greater than 50 wt% olefins, preferably greater than 80 wt% olefins.

In a specific embodiment, the olefin-containing stream separated by the separation system can be further separated by the olefin separation system, so that the olefin-containing stream is concentrated, the olefin content in the olefin-containing stream returned to the catalytic conversion reactor is increased, and the yield and selectivity of ethylene, propylene and butylene can be increased.

Referring to fig. 1, a first embodiment provides a catalytic conversion process for producing ethylene, propylene and butylene comprising:

in the first reaction zone I, a pre-lifting medium enters from the bottom of a reactor 2 through a pipeline 1, a regenerated catalytic conversion catalyst from a pipeline 17 moves upwards in an accelerated manner along the catalytic conversion reactor 2 under the lifting action of the pre-lifting medium, a raw material rich in olefin (the content of the olefin is more than or equal to 50 percent) is injected into the bottom of the reactor 2 together with atomized steam from a pipeline 4 through a pipeline 3, reacts and continues to move upwards;

in the second reaction zone II, the heavy feed oil is injected into the lower middle part of the catalytic conversion reactor 2 through a pipeline 5 together with the atomized steam from a pipeline 6, and is mixed with the material flow from the first reaction zone in the catalytic conversion reactor 2, and the feed oil reacts on a hot catalyst and moves upwards in an accelerated manner.

The generated reaction product and the inactivated spent catalyst enter a cyclone separator in a settler 8 through an outlet section 7 to realize the separation of the spent catalyst and the reaction product, the reaction product enters an air collection chamber 9, and the fine catalyst powder returns to the settler through a dipleg. Spent catalyst in the settler flows to the stripping section 10 where it is contacted with stripping steam from line 11. Oil gas stripped from the spent catalyst enters a gas collection chamber 9 after passing through a cyclone separator. The stripped spent catalyst enters a regenerator 13 through an inclined pipe 12, and main air enters the regenerator through a pipeline 16 to burn off coke on the spent catalyst so as to regenerate the inactivated spent catalyst. The smoke enters the cigarette machine through a pipeline 15. The regenerated catalyst enters the riser via line 17.

Reaction products (reaction oil gas) enter a subsequent product separation device 20 through a large oil gas pipeline 19, hydrogen, methane and ethane obtained by separation are led out through a pipeline 21, ethylene is led out through a pipeline 22, propylene is led out through a pipeline 23, butylene is led out through a pipeline 24, propane and butane are led out through a pipeline 25, first catalytic cracking distillate oil is led into an olefin separation device 28 through a pipeline 26, a material flow without olefin obtained by separation is led out through a pipeline 29, a material flow rich in olefin is led into the bottom of the first reaction zone I through a pipeline 30 to continue reacting, second catalytic cracking distillate oil is led into a hydrotreating reactor 14 through a pipeline 27, a light component after hydrotreating is led out through a pipeline 18, and second catalytic cracking distillate oil is led into the second reaction zone II through a pipeline 32 to continue reacting.

Referring to fig. 2, a second embodiment of the present disclosure provides a catalytic conversion process for producing ethylene, propylene and butylene, comprising:

the pre-lifting medium enters from the first reaction zone of the catalytic conversion reactor 2 through a pipeline 1, the regenerated catalytic conversion catalyst from a pipeline 17 moves upwards in an accelerated manner along the reactor 2 under the lifting action of the pre-lifting medium, the raw material rich in olefin is injected into the bottom of the first reaction zone of the reactor 2 through a pipeline 3 together with the atomized steam from a pipeline 4, the heavy raw oil is injected into the bottom of the second reaction zone of the reactor 2 through a pipeline 5 together with the atomized steam from a pipeline 6 to be mixed with the existing material flow of the reactor 2, and the raw oil reacts on the hot catalyst and moves upwards in an accelerated manner. The generated reaction product and the inactivated spent catalyst enter a cyclone separator in a settler 8 through an outlet section 7 to realize the separation of the spent catalyst and the reaction product, the reaction product enters an air collection chamber 9, and the fine catalyst powder returns to the settler through a dipleg. Spent catalyst in the settler flows to the stripping section 10 and contacts stripping steam from line 11. Oil gas stripped from the spent catalyst enters a gas collecting chamber 9 after passing through a cyclone separator. The stripped spent catalyst enters a regenerator 13 through an inclined pipe 12, and main air enters the regenerator through a pipeline 16 to burn coke on the spent catalyst so as to regenerate the inactivated spent catalyst. The smoke enters the cigarette machine through a pipeline 15. The regenerated catalyst enters the riser via line 17. The reaction product enters a subsequent separation device 20 through a large oil gas pipeline 19, the separated hydrogen, methane and ethane are led out through a pipeline 21, the ethylene is led out through a pipeline 22, the propylene is led out through a pipeline 23, the propane and the butane are led out through a pipeline 25, the first catalytic cracking distillate oil is led into an olefin separation device 28 through a pipeline 26, the separated material flow without olefin is led out through a pipeline 29, the first olefin-containing material flow separated by the olefin separation device 28 is led into the first reaction zone I of the catalytic conversion reactor 2 through a pipeline 30 for continuous reaction, the second olefin-containing material flow separated by the olefin separation device 28 is led into the third reaction zone III of the catalytic conversion reactor 2 through a pipeline 31 for continuous reaction. The second catalytic cracking distillate oil is led into the hydrotreating reactor 14 through a pipeline 27, the light component after hydrotreating is led out through a pipeline 18, and the hydrocracking distillate oil is led into the bottom of the second reaction zone II of the reactor 2 through a pipeline 32 for continuous reaction.

The present disclosure is further illustrated by the following examples. The raw materials used in the examples are all available from commercial sources.

1. The feedstocks I and II used in the examples of the present disclosure are heavy raw oils (heavy oils I and II), and the properties are shown in tables 1-1 and tables 1-2 below.

TABLE 1-1 (heavy oil I)

TABLE 1-2 (heavy oil II)

2. The catalyst i adopted by the present disclosure is prepared by the following preparation method:

969 g of halloysite (a product of China Kaolin company, with the solid content of 73%) is pulped by 4300 g of decationized water, 781 g of pseudoboehmite (a product of Shandong Zibo aluminum plant, with the solid content of 64%) and 144 ml of hydrochloric acid (with the concentration of 30% and the specific gravity of 1.56) are added and stirred evenly, the mixture is kept stand and aged for 1 hour at the temperature of 60 ℃, the pH value is kept between 2 and 4, the temperature is reduced to the normal temperature, and 5000 g of prepared slurry is added, wherein 1600g of a medium-pore ZSM-5 molecular sieve and a macroporous Y-shaped molecular sieve (produced by China petrochemical catalyst Qilu division) are added, and the weight ratio of the medium-pore ZSM-5 molecular sieve to the macroporous Y-shaped molecular sieve is 9: 1. Stirring uniformly, spray drying, washing off free Na + to obtain the catalyst. The catalyst obtained was aged at 800 ℃ under 100% steam, and the aged catalyst was referred to as catalyst i, the properties of which are shown in Table 2.

2. The catalyst ii adopted in the present disclosure has a commercial brand of CEP-1, is an industrial product produced by the china petrochemical catalyst zilu division, and the catalyst properties are shown in table 2.

3. The catalyst iii employed in this disclosure is sold under the trade designation CHP-1, a commercial product of China petrochemical catalyst, Qilu division, Inc., and has the catalyst properties shown in Table 2.

4. The catalyst iv adopted by the disclosure is prepared by the following preparation method:

ammonium metatungstate ((NH) was weighed₄)₂W₄O₁₃·18H₂O, chemically pure) and nickel nitrate (Ni (NO)₃)₂·18H₂O, chemically pure), 200 ml of solution was made with water. The solution was added to 50 g of alumina support, immersed at room temperature for 3 hours, the immersion liquid was treated with ultrasonic waves for 30 minutes during the immersion, cooled, filtered, and dried in a microwave oven for about 15 minutes. The catalyst comprises the following components: 30.0% by weight of WO₃L NiO in weight% and the balance alumina, catalyst iv.

5. The catalyst v adopted by the present disclosure is prepared by the following preparation method:

weighing 1000 g of pseudo-boehmite produced by China petrochemical catalyst ChangLing division, adding 1000 ml of aqueous solution containing 10 ml of nitric acid (chemical purity), extruding and molding on a double-screw extruder, drying at 120 ℃ for 4 hours, and roasting at 800 ℃ for 4 hours to obtain the catalyst carrier. Dipping for 2 hours by 900 ml of aqueous solution containing 120 g of ammonium fluoride, drying for 3 hours at 120 ℃, and roasting for 3 hours at 600 ℃; after cooling to room temperature, the catalyst was immersed in 950 ml of an aqueous solution containing 133 g of ammonium metatolybdate for 3 hours, dried at 120 ℃ for 3 hours, and calcined at 600 ℃ for 3 hours, and after cooling to room temperature, the catalyst was immersed in 900 ml of an aqueous solution containing 180 g of nickel nitrate and 320 g of ammonium metatungstate for 4 hours, and the fluorinated alumina support was immersed in a mixed aqueous solution containing 0.1 wt% of ammonium metatolybdate (chemical purity) and 0.1 wt% of nickel nitrate (chemical purity) with respect to the catalyst support for 4 hours, dried at 120 ℃ for 3 hours, and calcined at 600 ℃ for 4 hours, to obtain a catalyst v.

The i-iii properties of the above catalysts are shown in Table 2 below:

TABLE 2

In examples 1 to 4 and comparative examples 1 to 3 described below, ethylene, propylene and butene were obtained by the flow shown in FIG. 1; example 5 preparation of ethylene, propylene and butene using the flow scheme shown in FIG. 2

Example 1

Referring to the flow scheme shown in FIG. 1, the experiments were conducted on a pilot plant of riser reactors.

Contacting 1-pentene and a high-temperature catalytic conversion catalyst i at the bottom of a first reaction zone, wherein the reaction temperature is 700 ℃, the reaction pressure is 0.1MPa, the reaction time is 5 seconds, and the weight ratio of the catalyst to raw materials is 45: 1 under the condition of the catalyst;

heavy oil I is contacted with the material flow from the first reaction zone at the bottom of the second reaction zone, the heavy oil I and a catalytic conversion catalyst I are reacted at the temperature of 530 ℃, the pressure of 0.1MPa and the reaction time of 6 seconds, and the weight ratio of the catalyst to the raw materials is 5: 1, catalytic conversion reaction is carried out, and the weight ratio of 1-pentene to heavy oil I is 1: 9.

separating reaction products and spent catalyst of the reaction, introducing the spent catalyst into a regenerator for coke burning regeneration, introducing the obtained reaction products into a combined separation system to obtain products comprising ethylene, propylene, butylene, a material flow rich in olefin, second catalytic cracking distillate oil with the boiling point of more than 250 ℃ and the like, wherein the second catalytic cracking distillate oil and the hydrogenation catalyst iv have the hydrogen partial pressure of 18MPa at 350 ℃, and the volume space velocity of 1.5 hours^-1And reacting under the condition that the volume ratio of hydrogen to oil is 1500 to obtain the hydrocatalytically cracked distillate oil.

Introducing the separated material flow rich in olefin into the bottom of a first reaction zone for cracking, wherein the reaction temperature is 700 ℃, and the reaction time is 5 seconds; and the hydrocatalytically cracked distillate oil is mixed with the heavy raw oil and then returns to the second reaction zone for continuous reaction. The reaction conditions and product distribution are listed in Table 3.

Comparative example 1

The experiment was carried out on a pilot plant of riser reactors using a similar reaction scheme to that of example 1. Contacting heavy oil I and a catalytic conversion catalyst I at the bottom of a second reaction zone, wherein the weight ratio of the catalyst to raw materials is 5: catalytic conversion reaction takes place at 1. Separating reaction products and spent catalyst of the reaction, introducing the spent catalyst into a regenerator for coke burning regeneration, introducing the reaction products into a combined separation system to obtain products such as ethylene, propylene, butylene and second catalytic cracking distillate oil with the boiling point of more than 250 ℃, wherein the second catalytic cracking distillate oil and a hydrogenation catalyst iv have the hydrogen partial pressure of 18MPa and the volume space velocity of 1.5 hours at 350 ℃, and the like^-1And reacting under the condition that the volume ratio of hydrogen to oil is 1500 to obtain the hydrocatalytically cracked distillate oil. Mixing the obtained hydrocatalytically cracked distillate oil with heavy raw oil, and returning the mixture to the second reaction zone for reaction. The reaction conditions and product distribution are listed in Table 3.

Example 2

Contacting heavy oil I and a catalytic conversion catalyst I at the bottom of a second reaction zone, wherein the weight ratio of the catalyst to raw materials is 5: 1, carrying out catalytic conversion reaction, separating reaction products of the reaction and spent catalyst, introducing the obtained spent catalyst into a regenerator together for scorching regeneration, introducing the obtained reaction products into a combined separation system together to obtain products such as ethylene, propylene, butylene, olefin-rich material flow, second catalytic cracking distillate oil with the boiling point of more than 250 ℃ and the like, wherein the second catalytic cracking distillate oil and the hydrogenation catalyst iv have the hydrogen partial pressure of 18MPa and the volume space velocity of 1.5 hours at 350 ℃, and the volume space velocity of 1.5 hours^-1And reacting under the condition that the volume ratio of hydrogen to oil is 1500 to obtain the hydrocatalytically cracked distillate oil. Introducing the obtained material flow rich in olefin into the bottom of a first reaction zone for cracking, wherein the reaction temperature is 700 ℃, and the reaction time is 5 seconds; the hydrocatalytically cracked distillate oil is mixed with heavy raw oil and then returns to the second reaction zone for reactionShould be used. The reaction conditions and product distribution are listed in table 3.

Comparative example 2

The test was carried out on a medium-sized unit of riser reactor, heavy oil I was contacted with catalytic conversion catalyst ii at the bottom of the riser at a reaction temperature of 610 ℃, with the weight ratio of catalyst to feedstock being 16.9: 1, the reaction pressure is 0.1MPa, the catalytic conversion reaction is carried out within 6 seconds, and the product is not subjected to hydrogenation treatment and continuous reaction. The reaction conditions and product distribution are listed in table 3.

Example 3

Substantially the same as in example 2 except that heavy oil II was used. The second catalytic cracking distillate oil with the boiling point of more than 250 ℃ is not subjected to deep hydrogenation treatment and is contacted with a hydrodesulfurization catalyst v in a hydrodesulfurization reactor under the conditions of reaction pressure of 6.0MPa, reaction temperature of 350 ℃, hydrogen-oil volume ratio of 350 and volume space velocity of 2.0 hours^-1Then the low-sulfur hydrocatalytic cracking distillate oil is obtained and is used as a light oil component. The reaction conditions and product distribution are listed in table 3.

Comparative example 3

The test was conducted on a medium-sized riser reactor, with heavy oil ii and catalytic conversion catalyst v in contact at the bottom of the riser at a reaction temperature of 530 ℃ and a catalyst to feedstock weight ratio of 5: 1, the reaction pressure is 0.1MPa, the reaction time is 6 seconds, and the hydrotreating is basically the same as that of the example 3. The reaction conditions and product distribution are listed in table 3.

Example 4

Substantially the same as in example 1 except that the reaction conditions shown in Table 3 were used.

TABLE 3

As can be seen from Table 3, compared with comparative examples 1-3, the catalytic conversion methods provided in examples 1-4 of the present application have higher yields of ethylene, propylene and butylene, and the total yield of three olefins can reach more than 50%; and with the increase of the cracking temperature, the yields of ethylene, propylene and butylene are higher, and when the olefins in the examples 1-3 are cracked at high temperature, the total yield of the ethylene, the propylene and the butylene in the products can reach more than 60 percent; and the more the olefin content of the raw material is, the better the effect is, when 1-pentene with 100 percent of olefin content is taken as the raw material rich in olefin (example 1), the ethylene content of the product is 11.43 percent, the propylene content is 26.92 percent, the butene content is 24.01 percent, and the total content of the three is up to 62.36 percent.

Example 5

Referring to the flow scheme shown in FIG. 2, the experiments were conducted on a pilot plant of riser reactors.

1-octene and high temperature catalytic conversion catalyst i are contacted at the bottom of the first reaction zone, the reaction temperature is 700 ℃, the reaction pressure is 0.1MPa, the reaction time is 5 seconds, and the weight ratio of the catalyst to the raw materials is 5: 1, catalytic conversion reaction; contacting heavy oil I and a catalytic conversion catalyst I at the bottom of a second reaction zone, wherein the weight ratio of the catalyst to raw materials is 5: 1, catalytic conversion reaction is carried out, and the weight ratio of the 1-octene to the heavy oil I is 1: 1.

separating reaction products and spent catalyst of the reaction, and introducing the obtained spent catalyst into a regenerator for coke burning regeneration; introducing the obtained reaction products (reaction oil gas) into a product separation device together to obtain ethylene, propylene, butylene, first catalytic cracking distillate oil and second catalytic cracking distillate oil;

the second catalytic cracking distillate oil and the hydrogenation catalyst iv are subjected to hydrogen partial pressure of 18MPa and volume space velocity of 1.5 hours at 350 DEG C^-1And reacting under the condition that the volume ratio of hydrogen to oil is 1500 to obtain the hydrocatalytically cracked distillate oil.

Feeding the first catalytic cracking distillate oil into the olefin separation device, and separating out a first olefin-containing material flow with the boiling point of less than 140 ℃ and a second olefin-containing material flow with the boiling point of more than 140 ℃ and less than 250 ℃; introducing the first olefin-containing material flow into the bottom of the first reaction zone for cracking, wherein the reaction temperature is 700 ℃, and the reaction time is 5 seconds; introducing the second olefin-containing material flow into the bottom of the third reaction zone for cracking, wherein the reaction temperature is 530 ℃, and the reaction time is 5 seconds; the hydrocatalytically cracked distillate oil is mixed with heavy raw oil and then returns to the second reaction zone for reaction. The product ethylene yield was 16.21%, the propylene yield was 27.06%, the butene yield was 20.49%, and the hydrogen + methane + ethane yield was only 4.21%. The yield of propylene and butylene is higher, and the yield of ethylene is further improved.

The preferred embodiments of the present disclosure have been described in detail above, however, the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present disclosure within the technical idea of the present disclosure, and these simple modifications all fall within the protection scope of the present disclosure.

It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. In order to avoid unnecessary repetition, various possible combinations will not be separately described in this disclosure.

In addition, any combination of various embodiments of the present disclosure may be made, and the same should be considered as the disclosure of the present disclosure as long as it does not depart from the gist of the present disclosure.

Claims

1. A catalytic conversion process for producing ethylene, propylene and butylene, the process comprising the steps of:

(1) contacting an olefin-rich feedstock containing greater than 50 wt% olefins with a catalytic conversion catalyst having a temperature greater than 650 ℃ in a first reaction zone of a catalytic conversion reactor under first catalytic conversion reaction conditions;

2. The method of claim 1, wherein the method further comprises: under the condition of hydrogenation reaction, the second catalytic cracking distillate oil is in contact reaction with a hydrogenation catalyst to obtain hydrogenated second catalytic cracking distillate oil, and the hydrogenated second catalytic cracking distillate oil is returned to the catalytic conversion reactor for continuous reaction.

3. The process of claim 2 wherein said hydrogenated second catalytically cracked distillate is returned to said second reaction zone of said catalytic conversion reactor for further reaction and said olefin-rich stream is returned to said first reaction zone of said catalytic conversion reactor for further reaction; wherein the first reaction zone is upstream of the second reaction zone in the direction of reaction feed flow.

4. The method of claim 3, wherein the separation system comprises a product fractionation unit and an olefin separation unit, the method comprising:

passing said first catalytically cracked distillate to said olefin separation unit to separate a first olefin containing stream and a second olefin containing stream; the cut point between the first olefin-containing stream and the second olefin-containing stream is any temperature between 140 ℃ and 200 ℃;

returning the first olefin-containing stream to the first reaction zone of the catalytic conversion reactor for continuous reaction, and returning the second olefin-containing stream to the third reaction zone of the catalytic conversion reactor for continuous reaction;

5. The process according to any one of claims 1 to 4, wherein the catalytic conversion reactor is a riser reactor, preferably a variable diameter riser reactor.

6. The method of claim 1, wherein the first catalytic conversion reaction conditions comprise:

the reaction temperature is 650-750 ℃, preferably 630-750 ℃, and more preferably 630-720 ℃;

the second catalytic conversion reaction conditions include:

7. the process of claim 2, wherein the hydrogenation reaction conditions comprise: hydrogen partial pressure of 3.0-20.0 MPa, reaction temperature of 300-45The hydrogen-oil volume ratio is 300-2000 at 0 ℃, and the volume space velocity is 0.1-3.0 hours^-1。

8. The method of claim 1, wherein the method further comprises: the spent catalyst is subjected to coke burning regeneration to obtain a regenerated catalyst; returning the regenerated catalyst to the first reaction zone of the catalytic conversion reactor as the catalytic conversion catalyst.

9. The process according to claim 1, wherein the olefin-rich feedstock has an olefin content of 80 wt% or more, preferably 90 wt% or more, more preferably a pure olefin feedstock; the olefins in the olefin-rich feedstock are selected from olefins having 5 or more carbon atoms;

the heavy oil is selected from petroleum hydrocarbon and/or mineral oil; the petroleum hydrocarbon is one or more selected from vacuum gas oil, atmospheric gas oil, coking gas oil, deasphalted oil, vacuum residue, atmospheric residue and heavy aromatic raffinate oil; the mineral oil is selected from one or more of coal liquefaction oil, oil sand oil and shale oil.

10. The method according to claim 1 or 9, wherein the olefin-rich feedstock is derived from at least one of a five or more carbon fraction from an alkane dehydrogenation unit, a five or more carbon fraction from a refinery catalytic cracking unit, a five or more carbon fraction from an ethylene plant steam cracking unit, an olefin-rich fraction from more than five carbon MTO by-products, and an olefin-rich fraction from more than five carbon MTP by-products;

11. The process of claim 1, wherein the catalytic conversion catalyst comprises 1 to 50 wt% molecular sieve, 5 to 99 wt% inorganic oxide, and 0 to 70 wt% clay, based on the total weight of the catalytic conversion catalyst;

12. The process of claim 2, wherein the hydrogenation catalyst comprises 20 to 90 wt% of a support, 10 to 80 wt% of a supported metal, and 0 to 10 wt% of an additive, based on the total weight of the hydrogenation catalyst;

wherein the carrier is alumina and/or amorphous silicon-aluminum, the additive is at least one of fluorine, phosphorus, titanium and platinum, and the load metal is a VIB group metal and/or a VIII group metal;

13. A process according to claim 1, wherein the olefin-rich stream comprises more than 50 wt% olefins, preferably more than 80 wt% olefins.