CN108238837B - Method for producing low-carbon olefin by catalytic cracking - Google Patents
Method for producing low-carbon olefin by catalytic cracking Download PDFInfo
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- CN108238837B CN108238837B CN201611229532.8A CN201611229532A CN108238837B CN 108238837 B CN108238837 B CN 108238837B CN 201611229532 A CN201611229532 A CN 201611229532A CN 108238837 B CN108238837 B CN 108238837B
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- 238000004523 catalytic cracking Methods 0.000 title claims abstract description 36
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 25
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 24
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 63
- 239000002808 molecular sieve Substances 0.000 claims abstract description 26
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 239000002245 particle Substances 0.000 claims abstract description 16
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 13
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 13
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 10
- 239000011259 mixed solution Substances 0.000 claims abstract description 9
- 238000009826 distribution Methods 0.000 claims abstract description 8
- 239000000376 reactant Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000000443 aerosol Substances 0.000 claims abstract description 3
- 239000002283 diesel fuel Substances 0.000 claims abstract description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 16
- 150000001336 alkenes Chemical class 0.000 claims description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 8
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 8
- 230000004048 modification Effects 0.000 claims description 7
- 238000012986 modification Methods 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 5
- 239000005977 Ethylene Substances 0.000 claims description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims 2
- -1 ethylene, propylene Chemical group 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 7
- 239000000047 product Substances 0.000 description 10
- 239000012895 dilution Substances 0.000 description 9
- 238000010790 dilution Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 238000005336 cracking Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000004227 thermal cracking Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000010793 Steam injection (oil industry) Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
- C07C4/06—Catalytic processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/20—C2-C4 olefins
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a method for producing low-carbon olefin by catalytic cracking, which comprises the following steps: modifying raw powder of a ZSM-5 type nano molecular sieve catalyst, blending the modified raw powder with naphtha or diesel oil to prepare a catalyst mixed solution in an aerosol state, introducing the catalyst mixed solution into a reactor through a nozzle, and uniformly dispersing the catalyst in a reactant, wherein the concentration content of the ZSM-5 type nano molecular sieve catalyst in the total hydrocarbon feeding amount is 200-400 ppm; and then the reactant and the ZSM-5 type nano molecular sieve catalyst are subjected to catalytic cracking reaction in a reactor to generate low-carbon olefin. The invention can effectively solve the problem that the catalytic cracking effect is poor due to the reduction of the specific surface area of catalyst particles caused by the wider particle size distribution of molecular sieve particles in the prior art.
Description
Technical Field
The invention relates to a method for producing low-carbon olefin. In particular to a process method for producing low-carbon olefin by catalytic cracking of light petroleum hydrocarbon.
Background
At present, in the petrochemical industry, catalysts are commonly used mainly because the catalysts can reduce reaction temperature, improve reaction selectivity, reduce byproduct generation amount and improve raw material utilization rate, and in the current petrochemical industry, thermal cracking technology is mainly adopted.
Document 200410101548.1 reports a catalytic cracking method, in which a nano molecular sieve catalyst is introduced into the existing thermal cracking process for preparing low-carbon olefins, and a mixed liquid containing an ultra-fine catalyst is introduced into a pipeline between a preheater and a reactor, so that light hydrocarbons are subjected to catalytic cracking reaction in the reactor to produce small-molecular carbon-chain olefins.
Document CN1712496A discloses a method for preparing low-carbon olefins by uniformly dispersing an ultra-fine heterogeneous catalyst in a hydrocarbon mixture containing C6-C8 alkanes and performing catalytic cracking reaction in a reactor in a gas phase sol state, such as: ethylene and propylene, and the diameter of the ultrafine catalyst particles is 1-1000 nm.
Although the two methods of the invention solve the problems that the catalyst is easy to form carbon, short in service cycle, and needs to be regenerated frequently in the fixed bed reaction process, the specific surface area of the catalyst particles is reduced due to the wider particle size distribution of the molecular sieve particles, so that the activity of the catalyst is reduced, and the catalytic cracking effect is poor.
Disclosure of Invention
The invention mainly aims to improve the yield of olefin products. Because the existing tubular reactor can not effectively control the selectivity of ethylene and propylene under the condition of the same cracking temperature and a certain dilution ratio; and the reaction depth is improved by introducing a catalyst system, and simultaneously, the selectivity of ethylene and propylene can be changed to a certain extent due to the catalytic selection function of the catalyst, and the product yield of ethylene and propylene can be adjusted.
The invention discloses a method for producing low-carbon olefin by catalytic cracking, which comprises the following steps: modifying raw powder of a ZSM-5 type nano molecular sieve catalyst, blending the modified raw powder with naphtha or diesel oil to prepare a catalyst mixed solution in an aerosol state, introducing the catalyst mixed solution into a reactor through a nozzle, and uniformly dispersing the catalyst in a reactant, wherein the concentration content of the ZSM-5 type nano molecular sieve catalyst in the total hydrocarbon feeding amount is 200-400 ppm; and then the reactant and the ZSM-5 type nano molecular sieve catalyst are subjected to catalytic cracking reaction in a reactor to generate low-carbon olefin.
The method for producing the low-carbon olefin by catalytic cracking is characterized in that the silica-alumina molar ratio of the ZSM-5 type nano molecular sieve catalyst is preferably 50-70, the particle size is preferably distributed between 190-210nm, and the specific surface area is preferably 490-500 m2/g。
The method for producing the low-carbon olefin by catalytic cracking is characterized in that the preferred Si/Al molar ratio of the ZSM-5 type nano molecular sieve catalyst is 60-65.
The method for producing the low-carbon olefin by catalytic cracking is characterized in that the modification treatment is preferably carried out by treating a ZSM-5 nano molecular sieve catalyst by using lanthanum nitrate and phosphoric acid.
The method for producing the low-carbon olefin by catalytic cracking is characterized in that the concentration content of the ZSM-5 nano molecular sieve catalyst in the total hydrocarbon feeding amount is preferably 290-310 ppm.
The method for producing the low-carbon olefin by catalytic cracking disclosed by the invention is characterized in that the temperature of the catalytic cracking reaction is preferably 800-840 ℃.
The method for producing the low-carbon olefin by catalytic cracking is characterized in that the pressure of the catalytic cracking reaction is preferably 80-100 KPa.
The method for producing the low-carbon olefin by catalytic cracking disclosed by the invention has the advantage that the residence time of the catalytic cracking reaction is preferably 0.197-0.210 s.
The modification treatment of the invention comprises the following steps:
(1) preparing a lanthanum nitrate solution with the concentration of 20-30 wt%;
(2) preparing a phosphoric acid solution with the concentration of 30-40 wt%;
(3) mixing the lanthanum nitrate solution and the phosphoric acid solution according to the volume ratio of 1: 1, mixing;
(3) putting the raw powder of the catalyst into a crucible;
(4) pouring the mixed solution of lanthanum nitrate and phosphoric acid into a crucible, and stirring by using a glass rod while pouring the mixed solution to fully impregnate the catalyst until the liquid level of the solution exceeds the original catalyst powder; and then putting the mixture into a constant-temperature water bath for soaking for 8 hours at the temperature of 60 ℃, then filtering the catalyst solution, feeding the filtered catalyst powder into a muffle furnace for incineration, keeping the incineration temperature constant at 120 ℃ for 2 hours, keeping the incineration temperature constant at 350 ℃ for 4 hours, and keeping the incineration temperature constant at 450 ℃ for 6 hours, thus finishing the modification treatment of the catalyst and obtaining the modified catalyst.
The ZSM-5 type nano molecular sieve catalyst raw powder with the silicon-aluminum molar ratio of 50-70 and uniform particle size distribution preferably has the silicon-aluminum molar ratio of 60-65, the particle size distribution of 190-210nm and the molecular sieve specific surface area of 490-500 m2The silica-alumina molar ratio of the conventional ZSM-5 molecular sieve is 35, and the specific surface area is 350m2The specific surface area of the ZSM-5 molecular sieve with the uniform particle size is 1.4-1.428 times of that of the common conventional nano ZSM-5 molecular sieve, and the high specific surface area enables the ZSM-5 molecular sieve to have higher activity.
The concentration content of the catalyst in the total hydrocarbon feeding amount is 200-400ppm, preferably 290-310 ppm, the temperature is 800-840 ℃, the reaction pressure is 80-100 KPa, and the residence time is 0.197-0.210 s.
The invention has the following beneficial effects:
the uniform particle catalyst is introduced in the invention, the catalyst has large surface area and high activity, under the same reaction condition, the cracking depth is larger, and the yield of the cracked gas product can be improved, so that the yield of the olefin product is increased;
because the concentration of the doped catalyst is very small, the influence on the severity of reaction conditions is not obvious, but because the catalyst is doped, the gas yield is improved, the yield of the dilute hydrocarbon product is improved, and the production cost is relatively reduced;
Detailed Description
The following examples illustrate the invention in detail: the present example is carried out on the premise of the technical solution of the present invention, and detailed embodiments and processes are given, but the scope of the present invention is not limited to the following examples, and the following examples do not indicate process parameters of specific conditions, and generally follow conventional conditions.
And preparing the catalyst into a solution with the concentration of about 10-30% by using naphtha. The catalyst solution system consists of a mixed solution stirring storage tank, a peristaltic pump or a plunger pump, a connecting pipe, a valve and a nozzle which extends into the main device pipeline and has the same medium flowing direction with the main device pipeline. The catalyst mixture injection position is on the main device pipeline after the dilution steam injection port, and the nozzle is arranged to ensure that the vaporization effect of the catalyst system is more ideal and the catalyst mixture is more uniformly dispersed into the vaporized raw material medium. The nozzle is a venturi type, but is introduced into the conduit in a manner different from conventional: the spray type is generally a direct spray type; in order to ensure the atomization effect, the invention adopts a mode consistent with the material flow direction.
In the actual production, the concentration of the catalyst in the total hydrocarbon feed is within the range of 200-400ppm, preferably 290-310 ppm, the cracking temperature is 800-840 ℃, the reaction pressure is 80-100 KPa, and the residence time is 0.197-0.210 s.
The dilution ratio is increased in a certain range, so that the selectivity of the dilute hydrocarbon product can be improved, the yield of the dilute hydrocarbon product is improved, the coking of a cracking furnace tube is reduced, and the corresponding cracking reaction depth is increased when the dilution ratio is increased. However, when the dilution ratio is increased to a certain extent, the energy consumption of the apparatus increases and the processing capacity decreases. In the present invention, the dilution ratio is not particularly limited, and is usually 0.50 to 0.70.
Example 1
Naphtha produced by Daqing crude oil is used as a raw material, and the composition of the naphtha is as follows (w%):
c42.45, C59.94, C622.3, C725.18, C825.73C912.09, C101.86, C110.07, C120.01. Wherein, the normal alkane is 35.17, the isoparaffin is 27.29, the alkene is 0.56, the cycloalkane is 31.8, the arene is 4.91, and the unknown substance is 0.24.
The operating conditions are as follows: the pyrolysis furnace exit temperature was 838 ℃, the cross-over temperature was 570 ℃, the reaction pressure was 85KPa, the dilution ratio was 0.5, the residence time was 0.202s, and the catalyst injection concentration was 300ppm in the total hydrocarbon feed.
Under the same other operation conditions, the same naphtha raw material is subjected to catalytic cracking reaction comparison by using the ZSM-5 catalyst with the particle size distribution of 190-210nm and the silica-alumina ratio of 62, which is used by the invention, and the conventional ZSM-5 catalyst on the basis of lanthanum nitrate and phosphoric acid modification treatment, and the product yield is shown in Table 1.
TABLE 1
Example 2
Cracking was carried out using hydrocracked tail oil as the feedstock according to the procedure of example 1.
The operating conditions are as follows: the cracking furnace outlet temperature was 825 deg.C, the cross-over temperature was 547 deg.C, the reaction pressure was 85KPa, the dilution ratio was 0.70, and the residence time was 0.205 s.
Under the same operation conditions, the same hydrocracking tail oil is subjected to catalytic cracking reaction comparison by using a ZSM-5 catalyst which is used in the invention and has the particle size distribution of 190-210nm and the silica-alumina ratio of 62 and a conventional ZSM-5 catalyst on the basis of modification treatment by lanthanum nitrate and phosphoric acid, and the product yield is shown in Table 2.
TABLE 2
Example 3
Cracking was carried out according to the procedure of example 1 starting from straight-run diesel.
The operating conditions are as follows: 810 ℃, a cross temperature of 543 ℃, a dilution ratio of 0.70, an operating pressure of 85KPa, a residence time of 0.205s,
under the same other operation conditions, the same straight-run diesel raw material is subjected to catalytic cracking reaction comparison by using the ZSM-5 catalyst with the particle size distribution of 190-210nm and the silica-alumina ratio of 62, which is used by the invention, and a conventional ZSM-5 catalyst on the basis of lanthanum nitrate and phosphoric acid modification treatment, and the product yield is shown in Table 3.
TABLE 3
Claims (7)
1. A method for producing low-carbon olefins by catalytic cracking comprises the following steps: modifying raw powder of a ZSM-5 type nano molecular sieve catalyst, blending the modified raw powder with naphtha or diesel oil to prepare a catalyst mixed solution in an aerosol state, introducing the catalyst mixed solution into a reactor through a nozzle, and uniformly dispersing the catalyst in a reactant, wherein the concentration content of the ZSM-5 type nano molecular sieve catalyst in the total hydrocarbon feeding amount is 200-400 ppm; then the reactant and the ZSM-5 type nanometer molecular sieve catalyst are subjected to catalytic cracking reaction in a reactor to generate low-carbon olefin,
wherein the lower olefins comprise ethylene, propylene, and butadiene, and the gas production rate of ethylene in the lower olefins is higher than the gas production rate of propylene in the lower olefins, and
the modification treatment is to treat the ZSM-5 nano molecular sieve catalyst by utilizing lanthanum nitrate and phosphoric acid.
2. The catalytic cracking method for producing light olefins according to claim 1, wherein the ZSM-5 type nano molecular sieve catalyst has a Si/Al molar ratio of 50-70, a particle size distribution of 190-210nm, and a specific surface area of 490-500 m2/g。
3. The method for producing low-carbon olefins by catalytic cracking according to claim 2, wherein the ZSM-5 type nano molecular sieve catalyst has a silica-alumina molar ratio of 60 to 65.
4. The method for producing light olefins by catalytic cracking according to claim 1, wherein the concentration of the ZSM-5 nano molecular sieve catalyst in the total hydrocarbon feed amount is 290-310 ppm.
5. The method for producing low-carbon olefins by catalytic cracking according to claim 1, wherein the temperature of the catalytic cracking reaction is 800-840 ℃.
6. The method for producing low-carbon olefins by catalytic cracking according to claim 1, wherein the pressure of the catalytic cracking reaction is 80-100 KPa.
7. The method for producing low-carbon olefins by catalytic cracking according to claim 1, wherein the residence time of the catalytic cracking reaction is 0.197 to 0.210 s.
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| CN111632616A (en) * | 2020-07-06 | 2020-09-08 | 中国石油化工股份有限公司 | Liquid catalyst and application thereof |
| CN111732076A (en) * | 2020-07-06 | 2020-10-02 | 中国石油化工股份有限公司 | Method for catalytically cracking hydrocarbons by using liquid catalyst |
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| CN101870634A (en) * | 2009-04-22 | 2010-10-27 | 中国科学院大连化学物理研究所 | Method for preparing light olefin and arene from saturated hydrocarbon |
| CN102533313A (en) * | 2010-12-16 | 2012-07-04 | 中国石油化工股份有限公司 | Method for preparing ethylene and propylene through catalytic cracking |
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|---|---|---|---|---|
| US7122500B2 (en) * | 2003-09-22 | 2006-10-17 | Exxonmobil Chemical Patents Inc. | Molecular sieve catalyst composition, its making and use in conversion processes |
| CN1290972C (en) * | 2004-06-25 | 2006-12-20 | 中国石油化工股份有限公司 | Catalytic crack |
| CN100338184C (en) * | 2004-12-23 | 2007-09-19 | 中国石油化工股份有限公司 | Catalytic cracking method |
| CN103319293B (en) * | 2012-03-20 | 2015-03-11 | 中国石油化工股份有限公司 | Method for preparing light olefins and gasoline by catalytically cracking petroleum hydrocarbons and employed catalyst |
-
2016
- 2016-12-27 CN CN201611229532.8A patent/CN108238837B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101870634A (en) * | 2009-04-22 | 2010-10-27 | 中国科学院大连化学物理研究所 | Method for preparing light olefin and arene from saturated hydrocarbon |
| CN102533313A (en) * | 2010-12-16 | 2012-07-04 | 中国石油化工股份有限公司 | Method for preparing ethylene and propylene through catalytic cracking |
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