CN107961743B - Fast fluidized bed reactor, device and method for preparing propylene and C4 hydrocarbons from oxygen-containing compounds - Google Patents
Fast fluidized bed reactor, device and method for preparing propylene and C4 hydrocarbons from oxygen-containing compounds Download PDFInfo
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/82—Phosphates
- C07C2529/84—Aluminophosphates containing other elements, e.g. metals, boron
- C07C2529/85—Silicoaluminophosphates (SAPO compounds)
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Abstract
The invention relates to a fast fluidized bed reactor, a device and a method for preparing propylene and C4 hydrocarbon from oxygen-containing compounds. The apparatus comprises a fast fluidized bed reactor and a fluidized bed regenerator for regenerating the catalyst. The method comprises the following steps: a) introducing a raw material containing an oxygen-containing compound into a dense-phase zone of a fast fluidized bed reactor from n reactor feeding distributors, and contacting the raw material with a catalyst to generate a material flow containing a target product and a carbon-containing spent catalyst; b) sending the material flow containing the target product from the fast fluidized bed reactor into a product separation system, separating to obtain propylene, C4 hydrocarbons, light components and other components, returning more than 70 wt.% of the light components to the dense phase zone of the fast fluidized bed reactor from the lowest reactor feeding distributor of the fast fluidized bed reactor, and performing alkylation reaction on ethylene and oxygen-containing compounds under the action of a catalyst to generate products such as propylene. The method and the device of the invention improve the reaction rate of the vinyl alkylation and have high productivity per unit volume of the reactor.
Description
Technical Field
The invention relates to the field of chemical catalysis, in particular to a method and a device for preparing propylene and C4 hydrocarbons from oxygen-containing compounds.
Background
Propylene and butadiene are important chemical raw materials, and are generally obtained from naphtha cracking and steam cracking. The main sources of propylene are ethylene co-production propylene and refinery by-product propylene, while the main source of butadiene is obtained by further processing the C4 by-product produced in the ethylene cracking process. In recent years, Methanol To Olefin (MTO) technology, Methanol To Propylene (MTP) technology, ethane dehydrogenation to ethylene technology, and propane dehydrogenation to propylene technology have been developed rapidly, and the global trend of light olefin feedstock is obvious, which leads to a shortage of C4 resource supply, so that it is necessary to develop a process capable of preparing propylene and C4 olefin with high selectivity, thereby meeting the market demand.
German Lurgi company develops a fixed bed methanol-to-olefin technology (WO2004/018089), which utilizes a ZSM-5 molecular sieve catalyst of southern chemical company to perform a methanol-to-olefin reaction in a fixed bed reactor, wherein the propylene selectivity is close to 70%, and byproducts are ethylene, liquefied petroleum gas and gasoline.
The DMTO technology developed by the large-scale continuous substance takes SAPO molecular sieve as a catalyst, a dense-phase circulating fluidized bed reactor is used, methanol aqueous solution is taken as a raw material, the yield of ethylene and propylene in the product is about 80 percent, and more than 10 percent of C4 hydrocarbon is byproduct.
Patent CN104098429A discloses a method for preparing propylene and C4 hydrocarbons from methanol by using a circulating fluidized bed, which uses a ZSM-5 catalyst, and is characterized in that the raw material methanol and most of C1, C2 and C5 hydrocarbons in the product are jointly fed into the circulating fluidized bed reactor, and propylene, C4 hydrocarbons, C6 hydrocarbons and by-products are recovered as final products.
Patent CN101177374B discloses a process for preparing olefins from methanol or dimethyl ether. The method comprises a methanol or dimethyl ether conversion reaction, an ethylene and methanol alkylation reaction and a catalytic cracking reaction of heavy components above C4. The conversion reaction of methanol or dimethyl ether and the alkylation reaction of ethylene and methanol adopt a catalyst 1 to complete the reaction in the same reactor; the catalytic cracking reaction of heavy components above C4 is completed in another reactor by using catalyst 2.
The processes disclosed in patents CN104098429A and CN101177374B have a common feature of increasing the selectivity of the target products (propylene and C4) by recycling light components (hydrocarbons with carbon number not more than 2). The main reaction of the light component recycle reaction is the alkylation reaction of ethylene and methanol.
Both the MTO reaction and the olefin alkylation reactions can use acidic molecular sieve catalysts, but the MTO reaction rate is much higher than the olefin alkylation reaction. Through researches, the fresh SAPO catalyst has high activity and is more beneficial to olefin alkylation reaction, and after the catalyst is deposited with carbon, the olefin alkylation reaction rate can be rapidly reduced.
Methanol is a feedstock for both the olefin alkylation reaction and the MTO reaction, and therefore, the olefin alkylation reaction is necessarily accompanied by the MTO reaction. The MTO reaction results in carbon build-up and reduced activity of the catalyst, which inhibits the olefin alkylation reaction. Increasing the olefin alkylation reaction rate reduces the light component content of the product gas and thus increases the capacity per unit volume of the reactor.
The methods disclosed in patents CN104098429A and CN101177374B do not relate to the reactor structure, nor do they specify the catalyst flow pattern, the raw material distribution pattern, etc. in the reactor. The method disclosed in patent CN101177374B uses SAPO catalyst, and the examples show that the mass ratio of methanol to light components is 1:10-20, so it can be seen that the content of light components is extremely high and the productivity per unit volume of the reactor is extremely low. The process disclosed in patent CN104098429A uses ZSM-5 catalyst, the content of hydrocarbons above C6 in the product is high, and the content of light components in the product gas is not disclosed in the process.
From the above analysis, the main reactions for preparing propylene and C4 hydrocarbons from methanol are MTO reaction and olefin alkylation reaction, and therefore, the key to improving the selectivity of propylene and C4 hydrocarbons is the catalyst design and reactor design. Avoiding suppression of the olefin alkylation reaction by MTO reaction through reactor optimization is one of the important methods to improve the economics of the methanol to propylene and C4 hydrocarbons process.
Disclosure of Invention
The invention provides a novel method and a device for improving the reaction rate of the vinyl alkylation, aiming at the problem of low reaction rate of the vinyl alkylation in the process of preparing propylene and C4 hydrocarbon from methanol. The method is used for producing propylene and C4 hydrocarbon by using oxygen-containing compounds, and has the advantages of high yield of propylene and C4 hydrocarbon and good economical efficiency of the process.
To achieve the above objects, in one aspect, the present invention provides a fast fluidized bed reactor (1) for producing propylene and C4 hydrocarbons from oxygenates, the fast fluidized bed reactor (1) comprising: a reactor shell (2), n reactor feeding distributors (3-1-3-n), a reactor gas-solid separator 1(4), a reactor gas-solid separator 2(5), a reactor heat extractor (6), a product gas outlet (7) and a reactor stripper (8), wherein the lower part of the fast fluidized bed reactor (1) is a dense phase zone, the upper part of the fast fluidized bed reactor (1) is a dilute phase zone, the n reactor feeding distributors (3-1-3-n) are arranged in the dense phase zone, the reactor heat extractor (6) is arranged inside or outside the reactor shell (2), the reactor gas-solid separator 1(4) and the reactor gas-solid separator 2(5) are arranged outside the reactor shell (2), the reactor gas-solid separator 1(4) is provided with a regenerated catalyst inlet, the catalyst outlet of the reactor gas-solid separator 1(4) is arranged at the bottom of the zone, the gas outlet of the reactor gas-solid separator 1(4) is arranged in the dilute phase zone, the inlet of the reactor gas-solid separator 2(5) is arranged in the dilute phase zone, the catalyst outlet of the reactor gas-solid separator 2(5) is arranged in the dense phase zone, the gas outlet of the reactor gas-solid separator 2(5) is connected with the product gas outlet (7), the reactor stripper (8) penetrates through the reactor shell (2) from outside to inside at the bottom of the fast fluidized bed reactor (1) and is opened in the dense phase zone of the fast fluidized bed reactor (1), the bottom of the reactor stripper (8) is provided with a reactor stripping gas inlet (9), and the bottom of the reactor stripper (8) is provided with a spent catalyst outlet.
In a preferred embodiment, n reactor feed distributors (3-1 to 3-n) of a fast fluidized bed reactor (1) are placed in the dense phase zone from bottom to top with 0< n < 10.
In a preferred embodiment, the level of the opening of the reactor stripper (8) inside the reactor shell (2) is higher than the level of the dense phase zone of 1/10 to avoid fresh catalyst entering the reactor stripper directly.
In a preferred embodiment, reactor gas-solid separators 1(4) and reactor gas-solid separators 2(5) are cyclones.
The invention further provides an apparatus for the production of propylene and C4 hydrocarbons from oxygenates, comprising the above fast fluidized bed reactor (1) and a fluidized bed regenerator (14) for regenerating the catalyst.
In a preferred embodiment, the fluidized bed regenerator (14) is a turbulent fluidized bed regenerator.
In a preferred embodiment, the fluidized bed regenerator (14) comprises a regenerator housing (15), a regenerator feed distributor (16), a regenerator gas-solid separator (17), a regenerator heat extractor (18), a flue gas outlet (19) and a regenerator stripper (20), the lower part of the fluidized bed regenerator (14) is a regeneration zone, the upper part of the fluidized bed regenerator (14) is a settling zone, a regenerator feed distributor (16) is arranged at the bottom of the regeneration zone, a regenerator heat extractor (18) is arranged in the regeneration zone, a regenerator gas-solid separator (17) is arranged outside the settling zone or a regenerator shell (15), an inlet of the regenerator gas-solid separator (17) is arranged in the settling zone, a catalyst outlet of the regenerator gas-solid separator (17) is arranged in the regeneration zone, a gas outlet of the regenerator gas-solid separator (17) is connected with a flue gas outlet (19), and a regenerator stripper (20) is opened at the bottom of the regenerator shell (15);
a spent catalyst outlet of a reactor stripper (8) is connected with an inlet of a spent inclined tube (10), a spent slide valve (11) is arranged in the spent inclined tube (10), an outlet of the spent inclined tube (10) is connected with an inlet of a spent riser (12), a spent lifting gas inlet (13) is arranged at the bottom of the spent riser (12), and an outlet of the spent riser (12) is connected with a settling zone of a fluidized bed regenerator (14); and is
The bottom of the regenerator stripper (20) is provided with a regenerator stripping gas inlet (21), the bottom of the regenerator stripper (20) is connected with the inlet of a regeneration inclined tube (22), a regeneration slide valve (23) is arranged in the regeneration inclined tube (22), the outlet of the regeneration inclined tube (22) is connected with the inlet of a regeneration lifting tube (24), the bottom of the regeneration lifting tube (24) is provided with a regeneration lifting gas inlet (25), and the outlet of the regeneration lifting tube (24) is connected with the regenerated catalyst inlet of the reactor gas-solid separator 1 (4).
In a preferred embodiment, the regenerator gas-solid separator (17) is a cyclone separator.
In another aspect, the present invention provides a process for producing propylene and C4 hydrocarbons from oxygenates, comprising:
introducing a raw material containing oxygen-containing compounds into a dense-phase zone of a fast fluidized bed reactor (1) from n reactor feeding distributors (3-1-3-n), and contacting with a catalyst to generate a material flow containing propylene and C4 hydrocarbon products and a carbon-containing spent catalyst;
sending a stream containing propylene and C4 hydrocarbon products flowing out of the fast fluidized bed reactor (1) into a product separation system, and separating to obtain propylene, C4 hydrocarbons, light components, propane and hydrocarbons above C5, wherein the light components comprise more than 90 wt% of ethylene and also comprise small amounts of methane, ethane, hydrogen, CO and CO2More than 70 wt.% of the light components are returned to the dense phase zone of the fast fluidized bed reactor (1) from the lowermost reactor feed distributor (3-1) of the fast fluidized bed reactor (1), and the alkylation reaction of ethylene and the oxygenate is carried out under the action of the catalyst to generate a product containing propylene;
the spent catalyst is regenerated by a fluidized bed regenerator (14), and the regenerated catalyst enters the bottom of a dense phase zone in the fast fluidized bed reactor (1) after gas-solid separation by a gas-solid separator (1) and a reactor (4).
In a preferred embodiment, the process of the present invention is carried out using the above-described apparatus for the production of propylene and C4 hydrocarbons from oxygenates.
In a preferred embodiment, the spent catalyst enters a settling zone of a fluidized bed regenerator (14) through a reactor stripper (8), a spent inclined tube (10), a spent slide valve (11) and a spent riser (12);
the regeneration medium is introduced into a regeneration zone of the fluidized bed regenerator (14) from a regenerator feeding distributor (16) and reacts with the spent catalyst by burning carbon to generate CO and CO2The flue gas and the regenerated catalyst are discharged after being dedusted by a gas-solid separator (17) of the regenerator;
the regenerated catalyst enters the inlet of a gas-solid separator 1(4) of the reactor through a regenerator stripper (20), a regeneration inclined tube (22), a regeneration slide valve (23) and a regeneration lifting tube (24), and after the gas-solid separation, the regenerated catalyst enters the bottom of a dense phase zone in the fast fluidized bed reactor (1);
the stripping gas of the reactor enters a stripper (8) of the reactor from a stripping gas inlet (9) of the reactor to be in countercurrent contact with the spent catalyst, and then enters a fast fluidized bed reactor (1); spent lifting gas enters a spent lifting pipe (12) from a spent lifting gas inlet (13) to be in concurrent flow contact with a spent catalyst, and then enters a settling zone of a fluidized bed regenerator (14);
the regenerator stripping gas enters a regenerator stripper (20) from a regenerator stripping gas inlet (21) to be in countercurrent contact with the regenerated catalyst and then enters a fluidized bed regenerator (14); the regenerated lift gas enters a regenerated lift pipe (24) from a regenerated lift gas inlet (25) to be contacted with the regenerated catalyst in a concurrent flow manner, and then enters an inlet of a gas-solid separator 1(4) of the reactor.
The fast fluidized bed reactor of the present invention features that light component is fed via the lowest reactor material distributor, oxygen containing compound is fed via n reactor material distributors separately, and regenerated catalyst is fed directly to the bottom of the dense phase zone. On one hand, the catalyst has high activity at the lower part of the dense phase zone, which is beneficial to the alkylation reaction of ethylene, propylene and methanol; on the other hand, because the mode of multistage feeding of the oxygen-containing compound is adopted, the oxygen-containing compound is prevented from completing most of conversion reactions in a small part of area below the dense-phase area, so that the concentration of the oxygen-containing compound in most of the dense-phase area is uniform, and the inhibition of MTO reaction on the olefin alkylation reaction is weakened. Therefore, the fast fluidized bed reactor can effectively improve the reaction rate of the olefin alkylation, and the yield of the reactor per unit volume is high.
In the method for preparing propylene and C4 hydrocarbons by using the oxygen-containing compound, products such as ethylene, propylene and the like are generated by MTO reaction, ethylene, propylene and the like are consumed by olefin alkylation reaction, the rate of the ethylene alkylation reaction is high, and the light component content and the light component circulation amount in product gas are low. In the process of the invention, the light component recycle is from 5 to 40 wt.% of the oxygenate feed.
In the process of the present invention, more than 70 wt.% of the light components are recycled in the system, and the rate of release of the light components affects the composition of the product gas at equilibrium. At equilibrium, the composition of the product gas is 20-50 wt.% propylene, 15-40 wt.% C4 hydrocarbons, 10-45 wt.% light components, 0-5 wt.% propane, and 5-20 wt.% hydrocarbons above C5. The light components contain more than 90 wt.%, e.g. > 95 wt.% of ethylene, and the other components are methane, ethane, hydrogen, CO and CO2And the like.
In a preferred embodiment, the catalyst contains SAPO molecular sieve, and the catalyst has the functions of preparing olefin by methanol and alkylating olefin.
In a preferred embodiment, the regenerated catalyst carbon content is <2 wt.%, further preferably the regenerated catalyst carbon content is <0.5 wt.%.
In a preferred embodiment, the spent catalyst carbon content is 5-12 wt.%, and further preferably, the spent catalyst carbon content is 5-10 wt.%.
In a preferred embodiment, the dense phase zone reaction conditions of the fast fluidized bed reactor (1) are as follows: the apparent linear velocity of the gas is 1.0-8.0m/s, the reaction temperature is 300-550 ℃, the reaction pressure is 100-500kPa, and the bed density is 50-500kg/m3。
In a preferred embodiment, the fluidized bed regenerator (14) regeneration zone reaction conditions are: the apparent linear velocity of the gas is 0.1-2m/s, the regeneration temperature is 500-750 ℃, the regeneration pressure is 100-500kPa, and the bed density is 200-1200kg/m3。
In a preferred embodiment, the oxygenate is methanol and/or dimethyl ether; the regeneration medium is any one or a mixture of any more of air, oxygen-deficient air or water vapor; the reactor stripping gas, the regenerator stripping gas, the to-be-generated lifting gas and the regeneration lifting gas are water vapor or nitrogen.
Drawings
Fig. 1 is a schematic diagram of an apparatus for producing propylene and C4 hydrocarbons from oxygenates according to one embodiment of the invention.
The reference numerals in the drawings are explained below:
1-a fast fluidized bed reactor; 2-a reactor shell; 3-a reactor feed distributor (3-1 to 3-n); 4-reactor gas-solid separator 1; 5-reactor gas-solid separator 2; 6-reactor heat extractor; 7-product gas outlet; 8-reactor stripper; 9-reactor stripping gas inlet; 10-a to-be-grown inclined pipe; 11-spent spool valve; 12-a spent riser; 13-a spent lift gas inlet; 14-a fluidized bed regenerator; 15-a regenerator housing; 16-a regenerator feed distributor; 17-regenerator gas-solid separator; 18-regenerator heat extractor; 19-a flue gas outlet; 20-a regenerator stripper; 21-a regenerator stripping gas inlet; 22-regeneration inclined tube; 23-a regenerative slide valve; 24-a regenerative riser; 25-regeneration lift gas inlet.
Detailed Description
In one embodiment, a schematic diagram of an apparatus for producing propylene, C4 hydrocarbons from oxygenates according to the present invention is shown in fig. 1, the apparatus comprising:
a) a fast fluidized bed reactor (1) comprises a reactor shell (2), n reactor feeding distributors (3-1-3-n, 0< n <10), a reactor gas-solid separator 1(4), a reactor gas-solid separator 2(5), a reactor heat extractor (6), a product gas outlet (7) and a reactor stripper (8), wherein the lower part of the fast fluidized bed reactor (1) is a dense-phase zone, the upper part of the fast fluidized bed reactor is a dilute-phase zone, the n reactor feeding distributors (3-1-3-n) are arranged in the dense-phase zone from bottom to top, 0< n <10, the reactor heat extractor (6) is arranged inside or outside the reactor shell (2), the reactor gas-solid separator (1), (4) and the reactor gas-solid separator 2(5) are arranged outside the reactor shell (2), the inlet of the reactor gas-solid separator 1(4) is connected with a regeneration riser (24), the catalyst outlet of the reactor gas-solid separator 1(4) is arranged at the bottom of the dense-phase zone, the gas outlet of the reactor gas-solid separator 1(4) is arranged in the dilute-phase zone, the inlet of the reactor gas-solid separator 2(5) is arranged at the top of the reactor shell (2), the catalyst outlet of the reactor gas-solid separator 2(5) is arranged in the dense-phase zone, the gas outlet of the reactor gas-solid separator 2(5) is connected with the product gas outlet (7), the inlet of the reactor stripper (8) is arranged in the dense-phase zone of the fast fluidized bed reactor (1), and the level of the inlet is higher than that of the dense-phase zone of 1/10;
b) a fluidized bed regenerator (14) comprising a regenerator housing (15), a regenerator feed distributor (16), a regenerator gas-solid separator (17), a regenerator heat remover (18), a flue gas outlet (19) and a regenerator stripper (20), the lower part of the fluidized bed regenerator (14) is a regeneration zone, the upper part of the fluidized bed regenerator (14) is a settling zone, a regenerator feed distributor (16) is arranged at the bottom of the regeneration zone, a regenerator heat extractor (18) is arranged in the regeneration zone, a regenerator gas-solid separator (17) is arranged outside the settling zone or a regenerator shell (15), an inlet of the regenerator gas-solid separator (17) is arranged in the settling zone, a catalyst outlet of the regenerator gas-solid separator (17) is arranged in the regeneration zone, a gas outlet of the regenerator gas-solid separator (17) is connected with a flue gas outlet (19), and an inlet of a regenerator stripper (20) is connected with the bottom of the regenerator shell (15);
c) the bottom of a reactor stripper (8) is provided with a reactor stripping gas inlet (9), the bottom of the reactor stripper (8) is connected with the inlet of a to-be-regenerated inclined pipe (10), a to-be-regenerated slide valve (11) is arranged in the to-be-regenerated inclined pipe (10), the outlet of the to-be-regenerated inclined pipe (10) is connected with the inlet of a to-be-regenerated lifting pipe (12), the bottom of the to-be-regenerated lifting pipe (12) is provided with a to-be-regenerated lifting gas inlet (13), and the outlet of the to-be-regenerated lifting pipe (12) is connected with a settling zone of a fluidized bed regenerator (14);
d) the bottom of the regenerator stripper (20) is provided with a regenerator stripping gas inlet (21), the bottom of the regenerator stripper (20) is connected with the inlet of a regeneration inclined tube (22), a regeneration slide valve (23) is arranged in the regeneration inclined tube (22), the outlet of the regeneration inclined tube (22) is connected with the inlet of a regeneration lifting tube (24), the bottom of the regeneration lifting tube (24) is provided with a regeneration lifting gas inlet (25), and the outlet of the regeneration lifting tube (24) is connected with the inlet of a reactor gas-solid separator 1 (4).
In the above embodiments, the fluidized bed regenerator (14) may be a turbulent fluidized bed regenerator; the reactor gas-solid separators 1(4), the reactor gas-solid separators 2(5), and the regenerator gas-solid separator (17) may be cyclones.
In one embodiment, the process for producing propylene, C4 hydrocarbons from oxygenates of the present invention comprises:
a) introducing a raw material containing oxygen-containing compounds into a dense-phase zone of a fast fluidized bed reactor (1) from n reactor feeding distributors (3-1-3-n), and contacting with a catalyst to generate a material flow containing propylene and C4 hydrocarbon products and a carbon-containing spent catalyst;
b) sending a material flow containing propylene and C4 hydrocarbon products flowing out of the fast fluidized bed reactor (1) into a product separation system, and separating to obtain propylene, C4 hydrocarbons, light components, propane and hydrocarbons above C5, wherein the main component of the light components is ethylene, and small amounts of methane, ethane, hydrogen, CO and CO are also contained2More than 70 wt.% of light components are returned to the dense phase zone of the fast fluidized bed reactor (1) from the lowest reactor feed distributor (3-1) of the fast fluidized bed reactor (1), the alkylation reaction of ethylene and oxygen-containing compounds is carried out under the action of a catalyst to generate products such as propylene, and less than 30 wt.% of light components are recovered as byproducts;
c) the spent catalyst enters a settling zone of a fluidized bed regenerator (14) through a reactor stripper (8), a spent inclined tube (10), a spent slide valve (11) and a spent riser (12);
d) introducing a regeneration medium into a regeneration zone of a fluidized bed regenerator (14) from a regenerator feed distributor (16), and carrying out a carbon burning reaction on the regeneration medium and a spent catalyst to generate a catalyst containing CO and CO2The flue gas and the regenerated catalyst are discharged after being dedusted by a gas-solid separator (17) of the regenerator;
e) the regenerated catalyst enters the inlet of a gas-solid separator 1(4) of the reactor through a regenerator stripper (20), a regeneration inclined tube (22), a regeneration slide valve (23) and a regeneration lifting tube (24), and after the gas-solid separation, the regenerated catalyst enters the bottom of a dense phase zone in the fast fluidized bed reactor (1);
f) the stripping gas of the reactor enters a stripper (8) of the reactor from a stripping gas inlet (9) of the reactor to be in countercurrent contact with the spent catalyst, and then enters a fast fluidized bed reactor (1); spent lifting gas enters a spent lifting pipe (12) from a spent lifting gas inlet (13) to be in concurrent flow contact with a spent catalyst, and then enters a settling zone of a fluidized bed regenerator (14);
g) the regenerator stripping gas enters a regenerator stripper (20) from a regenerator stripping gas inlet (21) to be in countercurrent contact with the regenerated catalyst and then enters a fluidized bed regenerator (14); the regenerated lift gas enters a regenerated lift pipe (24) from a regenerated lift gas inlet (25) to be contacted with the regenerated catalyst in a concurrent flow manner, and then enters an inlet of a gas-solid separator 1(4) of the reactor.
To better illustrate the invention and to facilitate the understanding of the technical solutions thereof, the comparative examples and typical but non-limiting examples of the invention are as follows:
example 1
In this case, the apparatus shown in FIG. 1 is used for comparison, but the reactor gas-solid separator 1(4) is not included in the fast fluidized bed reactor (1), and the regeneration riser (24) is directly connected to the dilute phase zone of the fast fluidized bed reactor (1).
The fast fluidized bed reactor (1) comprises 3 reactor feeding distributors (3-1-3), a reactor heat collector (6) is arranged outside a reactor shell (2), and the horizontal height of an inlet of a reactor stripper (8) is at the height of a dense phase zone of 2/3. The dense-phase zone reaction conditions of the fast fluidized bed reactor (1) are as follows: the superficial linear velocity of the gas is about 3.0m/s, the reaction temperature is about 400 ℃, the reaction pressure is about 150kPa, and the bed density is about 80kg/m3。
The reaction conditions of the regeneration zone of the fluidized bed regenerator (14) are as follows: the gas superficial linear velocity is about 1.0m/s, the regeneration temperature is about 650 ℃, the regeneration pressure is about 150kPa, and the bed density is about 350kg/m3。
The catalyst contains SAPO molecular sieve, the carbon content of the spent catalyst is about 7 percent, and the carbon content of the regenerated catalyst is close to 0.0 weight percent.
The oxygen-containing compound is methanol, and the regeneration medium is air; the reactor stripping gas, the regenerator stripping gas, the to-be-generated lifting gas and the regeneration lifting gas are water vapor.
The light components were recycled in an amount of 9 wt.% of the methanol feed, and 46 wt.% of the light components were recycled in the system.
The composition of the product gas discharged from the fast fluidized bed reactor (1) was: 35 wt.% propylene, 29 wt.% C4 hydrocarbons, 31 wt.% lights, 1 wt.% propane, and 4 wt.% hydrocarbons above C5. The light component contains 99 wt.% of ethylene and 1 wt.% of methane, ethane, hydrogen, CO2And the like.
The composition of the product gas discharged by the separation system is: 41 wt.% propylene, 34 wt.% C4 hydrocarbons, 19 wt.% light components, 1 wt.% propane and 5 wt.% hydrocarbons above C5.
Example 2
With the apparatus shown in FIG. 1, the fast fluidized bed reactor (1) contains 3 reactor feed distributors (3-1 to 3-3), the reactor heat remover (6) is placed outside the reactor shell (2), and the inlet of the reactor stripper (8) is at the level of the dense phase zone of 2/3. The dense-phase zone reaction conditions of the fast fluidized bed reactor (1) are as follows: the superficial linear velocity of the gas is about 3.0m/s, the reaction temperature is about 400 ℃, the reaction pressure is about 150kPa, and the bed density is about 80kg/m3。
The reaction conditions of the regeneration zone of the fluidized bed regenerator (14) are as follows: the gas superficial linear velocity is about 1.0m/s, the regeneration temperature is about 650 ℃, the regeneration pressure is about 150kPa, and the bed density is about 350kg/m3。
The catalyst contains SAPO molecular sieve, the carbon content of the spent catalyst is about 7 percent, and the carbon content of the regenerated catalyst is close to 0.0 weight percent.
The oxygen-containing compound is methanol, and the regeneration medium is air; the reactor stripping gas, the regenerator stripping gas, the to-be-generated lifting gas and the regeneration lifting gas are water vapor.
The light components were recycled in an amount of 9 wt.% of the methanol feed, and 95 wt.% of the light components were recycled in the system.
The composition of the product gas discharged from the fast fluidized bed reactor (1) was: 40 wt.% propylene, 34 wt.% C4 hydrocarbons, 19 wt.% lights, 2 wt.% propane and 5 wt.% hydrocarbons above C5. Light groupThe component contains 98 wt.% of ethylene and 2 wt.% of methane, ethane, hydrogen, CO and CO2And the like.
The composition of the product gas discharged by the separation system is: 49 wt.% propylene, 41 wt.% C4 hydrocarbons, 1 wt.% light components, 3 wt.% propane and 6 wt.% hydrocarbons above C5.
The only difference between this case and example 1 (comparative) is that the regenerated catalyst enters the bottom of the fast fluidized bed reactor and is first contacted with the light components, whereas the regenerated catalyst in example 1 enters the dilute phase zone of the fast fluidized bed reactor. Comparing this case with example 1, it can be known that the conversion rate of the light component can be greatly increased by contacting the light component with the catalyst first, and the light component discharged from the separation system in this case is only less than 6% of that in the comparative case, so the apparatus of the present invention effectively increases the reaction rate of the vinyl alkylation.
Example 3
With the apparatus shown in FIG. 1, the fast fluidized bed reactor (1) contains 4 reactor feed distributors (3-1 to 3-4), the reactor heat remover (6) is placed outside the reactor shell (2), and the inlet of the reactor stripper (8) is at the level of the dense phase zone of 3/4. The dense-phase zone reaction conditions of the fast fluidized bed reactor (1) are as follows: the superficial linear velocity of the gas is about 5.0m/s, the reaction temperature is about 360 ℃, the reaction pressure is about 200kPa, and the bed density is about 50kg/m3。
The reaction conditions of the regeneration zone of the fluidized bed regenerator (14) are as follows: the gas superficial linear velocity is about 1.2m/s, the regeneration temperature is about 700 ℃, the regeneration pressure is about 200kPa, and the bed density is about 300kg/m3。
The catalyst contains SAPO molecular sieve, the carbon content of the spent catalyst is about 8 percent, and the carbon content of the regenerated catalyst is about 0.1 percent by weight.
The oxygen-containing compound is methanol, and the regeneration medium is air; the reactor stripping gas, the regenerator stripping gas, the to-be-generated lifting gas and the regeneration lifting gas are water vapor.
The light components were recycled in an amount of 14 wt.% of the methanol feed, and 90 wt.% of the light components were recycled in the system.
Set of product gases discharged from a fast fluidized bed reactor (1)The method comprises the following steps: 38 wt.% propylene, 30 wt.% C4 hydrocarbons, 26 wt.% lights, 2 wt.% propane, and 4 wt.% hydrocarbons above C5. The light fraction contained 98 wt.% ethylene and 2 wt.% methane, ethane, hydrogen, CO2And the like.
The composition of the product gas discharged by the separation system is: 50 wt.% propylene, 39 wt.% C4 hydrocarbons, 3 wt.% lights, 3 wt.% propane, and 5 wt.% hydrocarbons above C5.
Example 4
With the apparatus shown in FIG. 1, the fast fluidized bed reactor (1) contains 6 reactor feed distributors (3-1 to 3-6), the reactor heat remover (6) is placed inside the reactor shell (2), and the inlet of the reactor stripper (8) has a horizontal height at the level of the dense phase zone of 5/6. The dense-phase zone reaction conditions of the fast fluidized bed reactor (1) are as follows: the superficial linear velocity of the gas is about 2.0m/s, the reaction temperature is about 450 ℃, the reaction pressure is about 250kPa, and the bed density is about 100kg/m3。
The reaction conditions of the regeneration zone of the fluidized bed regenerator (14) are as follows: the gas apparent linear velocity is about 1.5m/s, the regeneration temperature is about 700 ℃, the regeneration pressure is about 250kPa, and the bed density is about 250kg/m3。
The catalyst contained SAPO molecular sieve, spent catalyst carbon content was about 9% and regenerated catalyst carbon content was about 0.05 wt.%.
The oxygen-containing compound is dimethyl ether, and the regeneration medium is oxygen-poor air; the reactor stripping gas, the regenerator stripping gas, the to-be-generated lifting gas and the regeneration lifting gas are nitrogen.
The light components were recycled in an amount of 16 wt.% of the dimethyl ether feed, and 95 wt.% of the light components were recycled in the system.
The composition of the product gas discharged from the fast fluidized bed reactor (1) was: 37 wt.% propylene, 31 wt.% C4 hydrocarbons, 22 wt.% light components, 2 wt.% propane and 8 wt.% hydrocarbons above C5. The light component contained 97 wt.% ethylene and 3 wt.% methane, ethane, hydrogen, CO2And the like.
The composition of the product gas discharged by the separation system is: 47 wt.% propylene, 39 wt.% C4 hydrocarbons, 1 wt.% lights, 3 wt.% propane, and 10 wt.% hydrocarbons above C5.
The present invention has been described in detail above, but the present invention is not limited to the specific embodiments described herein. It will be understood by those skilled in the art that other modifications and variations may be made without departing from the scope of the invention. The scope of the invention is defined by the appended claims.
Claims (10)
1. An apparatus for the production of propylene and C4 hydrocarbons from oxygenates, said apparatus comprising a fast fluidized bed reactor and a fluidized bed regenerator for regenerating the catalyst,
wherein the fast fluidized bed reactor comprises: a reactor shell, n reactor feeding distributors, n is more than or equal to 3 and less than 10, a reactor gas-solid separator 1, a reactor gas-solid separator 2, a reactor heat extractor, a product gas outlet and a reactor stripper, wherein the lower part of the fast fluidized bed reactor is a dense phase zone, the upper part of the fast fluidized bed reactor is a dilute phase zone, the n reactor feeding distributors are arranged in the dense phase zone from bottom to top, a light component with ethylene as a main component enters from the lowermost reactor feeding distributor, an oxygen-containing compound enters from the n reactor feeding distributors respectively, the reactor heat extractor is arranged in or outside the reactor shell, the reactor gas-solid separator 1 and the reactor gas-solid separator 2 are arranged outside the reactor shell, the reactor gas-solid separator 1 is provided with a regenerated catalyst inlet, the catalyst outlet of the reactor gas-solid separator 1 is arranged at the bottom of the dense phase zone, the gas outlet of the reactor gas-solid separator 1 is arranged in the dilute phase zone, the inlet of the reactor gas-solid separator 2 is arranged in the dilute phase zone, the catalyst outlet of the reactor gas-solid separator 2 is arranged in the dense phase zone, the gas outlet of the reactor gas-solid separator 2 is connected with the product gas outlet, the reactor stripper passes through the reactor shell from outside to inside at the bottom of the fast fluidized bed reactor and opens in the dense phase zone of the fast fluidized bed reactor, the bottom of the reactor stripper is provided with a reactor stripping gas inlet, the bottom of the reactor stripper is provided with a spent catalyst outlet, the horizontal height of the opening of the reactor stripper in the reactor shell is higher than the height of the 1/10 dense phase zone and is less than or equal to the height of the 5/6 dense phase zone and lower than the height of the catalyst outlet of the reactor gas-solid separator 2 in the dense phase zone, and
the fluidized bed regenerator comprises a regenerator shell, a regenerator feeding distributor, a regenerator gas-solid separator, a regenerator heat extractor, a flue gas outlet and a regenerator stripper, wherein the lower part of the fluidized bed regenerator is a regeneration zone, the upper part of the fluidized bed regenerator is a settling zone, the regenerator feeding distributor is arranged at the bottom of the regeneration zone, the regenerator heat extractor is arranged in the regeneration zone, the regenerator gas-solid separator is arranged outside the settling zone or the regenerator shell, an inlet of the regenerator gas-solid separator is arranged in the settling zone, a catalyst outlet of the regenerator gas-solid separator is arranged in the regeneration zone, a gas outlet of the regenerator gas-solid separator is connected with the flue gas outlet, and the regenerator stripper is opened at the bottom of the regenerator shell;
a spent catalyst outlet of the reactor stripper is connected to an inlet of a spent inclined tube, a spent slide valve is arranged in the spent inclined tube, an outlet of the spent inclined tube is connected to an inlet of a spent riser, a spent lifting gas inlet is arranged at the bottom of the spent riser, and an outlet of the spent riser is connected to a settling zone of a fluidized bed regenerator; and is
The bottom of the regenerator stripper is provided with a regenerator stripping gas inlet, the bottom of the regenerator stripper is connected with the inlet of a regeneration inclined pipe, a regeneration slide valve is arranged in the regeneration inclined pipe, the outlet of the regeneration inclined pipe is connected with the inlet of a regeneration lifting pipe, the bottom of the regeneration lifting pipe is provided with a regeneration lifting gas inlet, and the outlet of the regeneration lifting pipe is connected with the regenerated catalyst inlet of the reactor gas-solid separator 1.
2. The apparatus of claim 1 wherein the reactor gas-solid separator 1 and reactor gas-solid separator 2 are cyclones.
3. The apparatus of claim 1, wherein the fluidized bed regenerator is a turbulent fluidized bed regenerator.
4. A process for producing propylene and C4 hydrocarbons from oxygenates comprising:
introducing an oxygen-containing compound into a dense-phase zone of a fast fluidized bed reactor from n reactor feed distributors, and contacting the oxygen-containing compound with a catalyst to generate a material flow containing propylene and C4 hydrocarbon products and a carbon-containing spent catalyst, wherein the n reactor feed distributors are arranged in the dense-phase zone from bottom to top, and n is more than or equal to 3 and less than 10;
sending a stream containing propylene and C4 hydrocarbon products flowing out of the fast fluidized bed reactor into a product separation system, and separating to obtain propylene, C4 hydrocarbons, light components, propane and hydrocarbons above C5, wherein the light components contain more than 90 wt% of ethylene and also contain small amounts of methane, ethane, hydrogen, CO and CO2More than 70 wt.% of the light components are returned to the dense phase zone of the fast fluidized bed reactor from the lowermost reactor feed distributor of the fast fluidized bed reactor, the ethylene and oxygenate are alkylated over the catalyst to produce a product comprising propylene, and the propylene produced is alkylated;
the spent catalyst is regenerated by a fluidized bed regenerator, the regenerated catalyst enters the bottom of a dense phase zone in the fast fluidized bed reactor after being subjected to gas-solid separation by a gas-solid separator 1 of the reactor,
wherein the method is performed using the device according to any one of claims 1 to 3.
5. The method of claim 4, wherein
The spent catalyst enters a settling zone of a fluidized bed regenerator through a reactor stripper, a spent inclined tube, a spent slide valve and a spent riser;
introducing the regeneration medium into the regeneration zone of the fluidized bed regenerator, and performing a carbon burning reaction with the spent catalyst to generate a catalyst containing CO and CO2The flue gas and the regenerated catalyst are discharged after being dedusted by a gas-solid separator of the regenerator;
the regenerated catalyst enters the inlet of a gas-solid separator 1 of the reactor through a regenerator stripper, a regeneration inclined pipe, a regeneration slide valve and a regeneration lifting pipe, and after the gas-solid separation, the regenerated catalyst enters the bottom of a dense-phase zone in the fast fluidized bed reactor;
the stripping gas of the reactor enters a stripper of the reactor from a stripping gas inlet of the reactor to be in countercurrent contact with the spent catalyst, and then enters a fast fluidized bed reactor; the spent lifting gas enters a spent lifting pipe from a spent lifting gas inlet to be in concurrent contact with a spent catalyst and then enters a settling zone of a fluidized bed regenerator;
the regenerator stripping gas enters a regenerator stripper from a regenerator stripping gas inlet to be in countercurrent contact with the regenerated catalyst and then enters a fluidized bed regenerator; the regenerated lift gas enters the regenerated lift pipe from the regenerated lift gas inlet to be in concurrent contact with the regenerated catalyst and then enters the inlet of the reactor gas-solid separator 1.
6. The process of claim 4, wherein the lights recycle is from 5 to 40 wt.% of the oxygenate feed.
7. The process of claim 4, wherein the spent catalyst carbon content is 5-12 wt.% and the regenerated catalyst carbon content is <2 wt.%.
8. The process of claim 5, wherein the oxygenate is methanol and/or dimethyl ether; and/or the regeneration medium is any one or a mixture of any several of air, oxygen-deficient air or water vapor; and/or the reactor stripping gas, the regenerator stripping gas, the spent stripping gas and the regenerated stripping gas are water vapor or nitrogen.
9. The process of claim 4 wherein the fast fluidized bed reactor dense phase zone reaction conditions are: the apparent linear velocity of the gas is 1.0-8.0m/s, the reaction temperature is 300-550 ℃, the reaction pressure is 100-500kPa, and the bed density is 50-500kg/m3。
10. The process of claim 4, wherein the fluidized bed regenerator regeneration zone reaction conditions are: the apparent linear velocity of the gas is 0.1-2m/s, the regeneration temperature is 500-750 ℃, the regeneration pressure is 100-500kPa, and the bed density is 200-1200kg/m3。
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| CN107961745B (en) * | 2016-10-19 | 2021-12-14 | 中国科学院大连化学物理研究所 | Turbulent fluidized bed reactor, device and method for preparing propylene and C4 hydrocarbons from oxygen-containing compounds |
| CN108786672B (en) * | 2017-04-27 | 2021-01-26 | 中国科学院大连化学物理研究所 | Method for preparing p-xylene and co-producing low-carbon olefin by using methanol and/or dimethyl ether and benzene |
| CN108794291B (en) | 2017-04-27 | 2020-11-27 | 中国科学院大连化学物理研究所 | Fluidized bed device and method for preparing p-xylene and co-producing low-carbon olefin by methanol and/or dimethyl ether and toluene |
| CN108786670B (en) | 2017-04-27 | 2021-01-26 | 中国科学院大连化学物理研究所 | Method for preparing p-xylene and co-producing low-carbon olefin by methanol and/or dimethyl ether and toluene |
| CN111905839B (en) * | 2019-05-10 | 2023-06-06 | 中国科学院大连化学物理研究所 | Partial regeneration method of catalyst for preparing olefin from methanol and/or dimethyl ether and method for preparing olefin from methanol and/or dimethyl ether |
| US11975315B2 (en) * | 2019-05-10 | 2024-05-07 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Method for partially regenerating catalyst for methanol and/or dimethyl ether-to-olefin and method for methanol and/or dimethyl ether-to-olefin |
| CN117138702A (en) * | 2019-09-26 | 2023-12-01 | 中国石油化工股份有限公司 | Feed distributor and method for converting byproduct mixed oxygen-containing compound in process of preparing olefin from methanol |
| WO2022077458A1 (en) * | 2020-10-16 | 2022-04-21 | 中国科学院大连化学物理研究所 | Coke-control reactor, device for preparing low-carbon olefins from oxygen-containing compound and use thereof |
| KR20230010737A (en) * | 2020-10-16 | 2023-01-19 | 달리안 인스티튜트 오브 케미컬 피직스, 차이니즈 아카데미 오브 사이언시즈 | Process for producing low carbon olefins from fluidized bed reactors, apparatus and oxygen containing compounds |
| CN114377729B (en) * | 2020-10-16 | 2023-11-21 | 中国科学院大连化学物理研究所 | Fluidized bed regenerator, device for preparing low-carbon olefin and application thereof |
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