CN1566267A - Catalytic pyrolysis process for producing petroleum hydrocarbon of ethylene and propylene - Google Patents
Catalytic pyrolysis process for producing petroleum hydrocarbon of ethylene and propylene Download PDFInfo
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Abstract
The invention discloses a catalytic pyrolysis process for producing petroleum hydrocarbon of ethylene and propylene which comprises, feeding preheated petroleum hydrocarbon raw material into lift tubes, contacting phosphor modified five-membered ring high silicon zeolite catalyst for reaction under the condition of catalytic thermal cracking, thus separating the reaction product and catalyst to be produced, then loading the reaction product into subsequent separation system for product separation, stripping and regenerating the catalyst, returning to reactor for circulation.
Description
Technical field
The present invention relates to a kind of petroleum hydrocarbon catalytic thermocracking process of producing ethene and propylene.
Background technology
The traditional method of producing ethene from petroleum hydrocarbon is the steam heat cracking process, and suitable raw material is light petroleum hydrocarbons such as ethane, propane, butane, Sweet natural gas, petroleum naphtha or solar oil.Along with crude oil becomes heavy day by day, the output of light petroleum hydrocarbon is restricted, so people come diversion to the technology of producing ethene from heavy petroleum hydrocarbon.For example adopt the heavy petroleum hydrocarbon pyrolysis method of inert solids such as quartz sand, coke, adopt basic metal or alkaline earth metal oxide catalyzer as the heavy petroleum hydrocarbon pyrolysis method of thermal barrier etc. as thermal barrier.The temperature of reaction of these methods all surpasses 800 ℃.
In recent years, some patent has been introduced the use solid acid catalyst under certain reaction type formula and operational condition, produces the method for low-carbon alkene from petroleum hydrocarbon.
For example, having disclosed with the ZSM-5 zeolite among the JP60-224428 is active ingredient, Al
2O
3Be the catalyzer of carrier, under 600～750 ℃ to C
5～C
25The paraffinic hydrocarbon raw material carry out catalytic cracking, C
2 =～C
4 =Productive rate is about 30m%.
Having disclosed among the USP3758403 with ZSM-5 zeolite and large pore zeolite (as X type, Y type) is that the productive rate that the catalyzer of active ingredient (ratio of the two is 1: 10～3: 1) can make propylene add butylene in the gasoline octane rating in improving product increases to about 10 heavy %.
Employing large pore zeolite and SiO have been reported among the USP5318696
2/ Al
2O
3The catalyzer of the mesopore zeolite with MFI structure less than 30 can be produced high-octane gasoline, also can improve low-carbon alkene simultaneously, especially the productive rate of propylene.
The mixture that has disclosed among the CN1004878B with ZSM-5 zeolite and y-type zeolite is the catalyzer of active ingredient, under 500～650 ℃ temperature of reaction, can when improving the product gasoline octane rating, improve the productive rate of light olefin, and be primary product wherein with propylene and butylene.
Many methods that zeolite with five-membered ring structure is carried out the modification processing have also been reported in the document, to improve the selectivity of reaction product.As introducing phosphorus in the zeolite that has five-membered ring structure at ZSM-5 etc. or/and metal ion, absorption and catalytic performance that can the modulation zeolite.
Reported among the USP4365104 with the method for P and Mg modified zsm-5 zeolite, its objective is that the molecular sieve with modification is used for xylene isomerization, to improve the selectivity of p-Xylol, introducing P and Mg mainly is in order to strengthen the shape selectivity energy of molecular sieve; But then, the reactive behavior of the acidity of molecular sieve and the hydrocarbon conversion then reduces after the modification.
Reported at SiO among the USP5236880
2/ Al
2O
3Greater than the paraffinic hydrocarbon cracking catalyst that adds VIIIB family metal component, preferred nickel in 5 the zeolite with MFI or MEL structure, this catalyzer can improve the paraffinic hydrocarbon conversion of raw material, increase the aromatic component in the gasoline fraction, improve the octane value and the gasoline yield of gasoline.
It is the catalyzer of active ingredient that USP5380690 and CN1093101A have disclosed with phosphorous and five-ring supersiliceous zeolite rare earth.This catalyzer hydro-thermal activity stability height under 580 ℃ reaction conditions, is high 4～7 units of catalyzer transformation efficiency of active ingredient with the HZSM-5 zeolite, C
2 =～C
4 =High 4～5 units of productive rate.
It is the catalyzer of active ingredient that CN1117518A has disclosed with phosphorous and five-ring supersiliceous zeolite and y-type zeolite mixture rare earth.Particularly propylene, iso-butylene and the high characteristics of isopentene productive rate of low-carbon alkene in this catalyzer hydro-thermal activity stability height, transformation efficiency height, the product.
In sum, do not relate to the processing method that employing five-ring high silica zeolite catalyst catalytic pyrolysis phosphorous and transition metal is produced low-carbon alkenes such as ethene, propylene in the prior art as yet.
Summary of the invention
The objective of the invention is to propose a kind of is raw material with the petroleum hydrocarbon, uses phosphorous and five-ring high silica zeolite catalyst transition metal, under the catalytic pyrolysis condition, produces the particularly method of ethene and propylene of low-carbon alkene.
The objective of the invention is to reach: will send in the riser reactor through the petroleum hydrocarbon raw material of preheating, and contact with the catalyzer that contains the five-ring supersiliceous zeolite of heat, and under the catalytic pyrolysis condition, react by following proposal; Reaction product isolated and reclaimable catalyst; Reaction product is sent into subsequent separation system and is carried out product separation, and reclaimable catalyst Returning reactor after stripping, regeneration recycles; Wherein, it is 0～70% clay, 5～99% inorganic oxide and 1～50% the zeolite of benchmark that described catalyzer contains with the catalyst weight, described zeolite is the five-ring supersiliceous zeolite of 75～100 heavy % and the y-type zeolite of 0～25 heavy %, and the phosphorous and transition metal M of described five-ring supersiliceous zeolite, its anhydrous chemical expression is counted (0～0.3) Na with the quality of oxide compound
2O (0.3～5) Al
2O
3(1.0～10) P
2O
5(0.7～15) M
xO
y(0～10) RE
2O
3(70～98) SiO
2, wherein, M is selected from one or both transition metal among Fe, Co, Ni, Cu, Zn, Mo or the Mn, and x is the valency of oxygen, and y is the valency of transition metal.
Compared with prior art, beneficial effect of the present invention is mainly reflected in following aspect:
1, compares with the fluid catalytic cracking of routine, the present invention has adopted the five-ring high silica zeolite catalyst of the phosphorous and transition metal that hydrogen transfer activity is low, ethylene selectivity is high, improved temperature of reaction, thereby increased the productive rate of low-carbon alkene, particularly increased the productive rate of ethene and propylene, for petrochemical complex provides more raw materials.
2, compare with the method for the catalytic cracking to prepare lower carbon olefin of prior art, the present invention adopted the five-ring high silica zeolite catalyst of riser reactor and the phosphorous and transition metal that olefine selective is good, lytic activity is high, improved the particularly productive rate of ethene and propylene of low-carbon alkene.
3, the present invention has been owing to found the operational condition of appropriate catalyst, reactor pattern and catalyzed reaction, thereby obtained than the higher low-carbon alkene productive rate of ethene particularly.
4, the wide scope of material of the present invention's use can be atmospheric gas oil, vacuum gas oil or its mixture, also can be residual oil or crude oil.
Specific embodiments
Concrete operations step of the present invention is as follows: petroleum hydrocarbon is sent in the riser reactor after preheating, contacting with the five-ring high silica zeolite catalyst of the phosphorous and transition metal of heat, is that 550～700 ℃, reaction pressure are that the weight ratio (hereinafter to be referred as agent-oil ratio) of 150～400 kPas, catalyzer and stock oil is 15～40 in temperature of reaction: 1, the weight ratio of water vapor and stock oil (hereinafter to be referred as water-oil ratio) is to carry out the catalytic pyrolysis reaction under 0.3～1: 1 the condition.Reaction product isolated and reclaimable catalyst.Behind chilling, further isolate gaseous product and the product liquids such as pyrolysis gasoline and cracking light oil that comprise ethene and propylene from the product that reactor is drawn.Reclaimable catalyst enters stripper, and the water steam stripped goes out on it hydrocarbon product of absorption, and reclaimable catalyst is admitted to revivifier then, contacts with the oxygen-containing gas of heat such as air and carries out coke burning regeneration.Catalyzer with water steam after the regeneration and/or the lighter hydrocarbons stripping that is rich in methane are removed and are turned back to the reactor internal recycle again behind the non-hydrocarbon gas impurity that adsorbs on it and carry and use.The regenerated catalyst of heat is supplied with the needed reaction heat of petroleum hydrocarbon catalytic pyrolysis, and reacted reclaimable catalyst when in revivifier, regenerating liberated heat absorb by regenerated catalyst, during the regenerated catalyst Returning reactor heat that absorbs is resupplied petroleum hydrocarbon raw material and carries out the catalytic pyrolysis reaction.
The used reaction product quenching medium of the present invention comprises cracking light oil, recycle stock, slurry oil and/or residual oil, and the chilling agent is injected into the reaction oil gas exit, cooled product logistics fast.
The used regenerated catalyst stripping medium of the present invention comprises water vapor and/or lighter hydrocarbons, preferably is rich in the lighter hydrocarbons of methane, the stripping medium is injected into the interior stripping of regenerator stripper and goes out the non-hydrocarbon gas impurity that adsorbs and carry on the regenerated catalyst, can subtract appropriate hydrocarbon gas purified difficulty like this.
The used petroleum hydrocarbon raw material of the present invention can be atmospheric gas oil, vacuum gas oil or its mixture, also can be residual oil or crude oil.The mode of raw material injecting reactor can adopt single-point to inject, and also can adopt multiple spot to inject.
The catalyzer that the present invention is used, contain in the catalyst weight is clay, 5～99% inorganic oxide and 1～50% the zeolite of benchmark 0～70%, wherein said zeolite is made up of the five-ring supersiliceous zeolite of 75～100 heavy % and the y-type zeolite of 0～25 heavy %, phosphorous and the transition metal M of wherein said five-ring supersiliceous zeolite, its anhydrous chemical expression is counted (0～0.3) Na with the quality of oxide compound
2O (0.3～5) Al
2O
3(1.0～10) P
2O
5(0.7～15) M
xO
y(0～10) RE
2O
3(70～98) SiO
2, wherein, M is selected from one or both transition metal among Fe, Co, Ni, Cu, Zn, Mo or the Mn, RE represents rare earth, and x is the valency of oxygen, and y is the valency of transition metal, wherein when if the valency of transition metal is even number, x is 1, and y is that the transition metal compound valency is divided by 2.
In the catalyzer of the present invention, described clay can be natural or synthetic, through or the various clays that are used as cracking catalyst carrier usually handled without various chemistry and/or physical method, as kaolin and halloysite etc.
In the catalyzer of the present invention, described inorganic oxide is selected from amorphous Si O
2Al
2O
3, Al
2O
3Or/and SiO
2
In the catalyzer of the present invention, described y-type zeolite prepares with various chemistry and/or physical method, for example hydrothermal method, method of chemical treatment (EDTA acidic treatment, ammonium silicofluoride aluminium-eliminating and silicon-replenishing method and SiCl
4Vapor phase process) or combine with chemical treatment method preparation of hydro-thermal, can contain or not contain rare earth; The y-type zeolite that wherein contains rare earth is Rare Earth Y (REY) or rare earth hydrogen Y (REHY).
In the catalyzer that the present invention adopts, phosphorous and transition metal M in the described five-ring supersiliceous zeolite, the quality in oxide compound is preferably (0～0.2) Na
2O (0.9～5) Al
2O
3(1.5～7) P
2O
5(0.9～10) M
xO
y(82～92) SiO
2Perhaps be (0～0.2) Na
2O (0.9～5) Al
2O
3(1.5～7) P
2O
5(0.9～10) M
xO
y(0.5～10) RE
2O
3(82～92) SiO
2
Transition metal M wherein has dehydrogenation functionality, is selected from one or both metals among Fe, Co, Ni, Cu, Zn, Mo or the Mn, one or both among preferred Fe, Co or the Ni, more preferably Fe and/or Ni.
Five-ring supersiliceous zeolite of the present invention, its preparation process comprises ammonia exchange, phosphorus modification, metal-modified and calcination process step usually.
The exchange of described ammonia be with the na-pretreated zeolite that contains or do not contain rare earth of conventional crystallization gained with MFI structure according to zeolite: ammonium salt: H
2O=1: (0.1～1): the weight ratio of (5～10) is at room temperature to 100 ℃ 0.3～1 hour after-filtration of exchange down, and na-pretreated zeolite wherein is if adopt organic formwork agent synthetic words, at first removed template method.Described ammonium salt can be selected from one of ammonium chloride, ammonium sulfate or ammonium nitrate or their mixture for inorganic ammonium salt commonly used.
Described with the phosphorus modification and metal-modified be to adopt the mode of dipping or ion-exchange to carry out.
Wherein said dipping can adopt following three kinds of modes again:
A. the filter cake after the ammonia exchange and the P contained compound aqueous solution of calculated amount are evenly dried in room temperature to 95 a ℃ making beating, after roasting under 400～800 ℃ of conditions, ℃ mix, dry in room temperature to 95 with the compound water solution that contains transition metal M of calculated amount again.
B. the P contained compound aqueous solution of filter cake after the ammonia exchange and calculated amount is evenly dried in room temperature to 95 a ℃ making beating, ℃ mix oven dry with the compound water solution that contains transition metal M of calculated amount in room temperature to 95 again, wherein reversed order that also can the above-mentioned two kinds of solution of dipping.
C. the mixed aqueous solution of the P contained compound of the filter cake after the ammonia exchange and calculated amount and the compound of transition metal M ℃ is mixed afterwards in room temperature to 95 and dry.
Wherein said ion-exchange is: the P contained compound aqueous solution of filter cake after the ammonia exchange and calculated amount is evenly dried in room temperature to 95 a ℃ making beating, after roasting under 400～800 ℃ of conditions, again with the compound water solution that contains transition metal M of calculated amount by 1: after the solid-to-liquid ratio of (5～20) mixes, at 80～95 ℃, pH=4～7 time 2～3 hours after-filtration of stirring, but repeated exchanged repeatedly, and exchange back gained samples with water is washed repeatedly, and oven dry gets final product.
Described P contained compound is selected from one of phosphoric acid, aluminum phosphate, ammonium hydrogen phosphate, primary ammonium phosphate or ammonium phosphate or its mixture.The compound of described transition metal M is selected from their water-soluble salt, described water-soluble salt is selected from muriate, nitrate or vitriol, for example ferric sulfate, ferrous sulfate, iron nitrate, iron(ic) chloride, iron protochloride, rose vitriol, Xiao Suangu, cobalt chloride, single nickel salt, nickelous nitrate or nickelous chloride.
The catalyzer that the present invention adopts, its preparation process is as follows: with the precursor of inorganic oxide, as pseudo-boehmite, aluminium colloidal sol, silicon sol or its mixture and silicon-aluminum sol or gel, mix by preset blending ratio with halloysite, and it is mixed with the slurries that solid content is 10～50 heavy % with decationized Y sieve water, stir, use the mineral acid example hydrochloric acid, nitric acid, phosphoric acid or sulfuric acid transfer to 2～4 with slurries PH, keep this pH value, add aluminium colloidal sol after leaving standstill aging 0～2 hour under 20～80 ℃, stirred 0.5～1.5 hour, the MFI structural zeolite and the y-type zeolite that add predetermined amount, homogeneous, spraying drying, the flush away free sodium ion, drying.
Following example will give further instruction to method provided by the invention, but therefore the present invention is not subjected to any restriction.Wherein employed catalyzer has following several in embodiment and the Comparative Examples:
Catalyst A is to consist of (being benchmark with the catalyst weight) according to what conventional production of cracking catalyst prepared: 18% five-ring supersiliceous zeolite, 27% aluminum oxide and surplus kaolin, wherein five-ring supersiliceous zeolite (is benchmark with zeolite weight) is 30 five-ring supersiliceous zeolite for containing 2.4% phosphorus oxide, 3.8% rare earth oxide and 1.5% ferric oxide, silica alumina ratio.
Catalyst B is to consist of (being benchmark with the catalyst weight) according to what conventional production of cracking catalyst prepared: 18% five-ring supersiliceous zeolite, 27% aluminum oxide and surplus kaolin, wherein five-ring supersiliceous zeolite (is benchmark with zeolite weight) is 60 five-ring supersiliceous zeolite for containing 4.1% phosphorus oxide, 1.0% ferric oxide and 1.0% nickel oxide, silica alumina ratio.
Catalyzer C consists of (being benchmark with the catalyst weight) according to what conventional production of cracking catalyst prepared: 15% five-ring supersiliceous zeolite, 5%REHY zeolite, 20% aluminum oxide, 6% amorphous aluminum silicide and surplus kaolin, wherein five-ring supersiliceous zeolite (is benchmark with zeolite weight) is 60 five-ring supersiliceous zeolite for containing 2.1% phosphorus oxide and 1.0% ferric oxide, silica alumina ratio.
Contrast medium A prepares according to the prescription of catalyst A and preparation method, and wherein the five-ring supersiliceous zeolite is that 30 five-ring supersiliceous zeolite substitutes with containing 2.4% phosphorus oxide and 3.8% rare earth oxide, silica alumina ratio.
Contrast medium B prepares according to the prescription of catalyst B and preparation method, and wherein the five-ring supersiliceous zeolite is that 60 five-ring supersiliceous zeolite substitutes with containing 4.1% phosphorus oxide, silica alumina ratio.
Contrast medium C prepares according to the prescription of catalyzer C and preparation method, and wherein the five-ring supersiliceous zeolite is that silica alumina ratio is 60 HZSM-5 zeolite.
Embodiment 1
This example explanation is phosphorous when use, during the catalyst A of the five-ring supersiliceous zeolite of rare earth and iron, method provided by the invention is produced the situation of ethene and propylene.
With proportion be 0.873, boiling range is that 350～540 ℃ vacuum gas oil is a raw material, is that 700 ℃, agent-oil ratio are that 25: 1, water-oil ratio are that 0.5: 1, weight hourly space velocity are 10h in temperature of reaction
-1Operational condition under, on small fixed flowing bed-tion reacting device, carry out catalytic pyrolysis test, it the results are shown in table 1.
Comparative Examples 1
This example explanation when the contrast medium A of the five-ring supersiliceous zeolite that uses phosphorous and rare earth, with embodiment 1 identical operations condition under the method that provides of prior art produce the situation of ethene and propylene, it the results are shown in table 1.
Table 1
| Catalyzer | Catalyst A | Contrast medium A |
| Product distributes, heavy % | ||
| Splitting gas | ????70.58 | ????69.86 |
| Wherein, ethene | ????25.23 | ????23.82 |
| Propylene | ????21.56 | ????19.85 |
| Butylene | ????5.23 | ????6.86 |
| Pyrolysis gasoline | ????11.63 | ????12.16 |
| Cracking light oil | ????3.61 | ????3.77 |
| Cracking heavy oil | ????3.06 | ????3.13 |
| Coke | ????11.12 | ????11.08 |
| Total gas olefins yield, heavy % | ????52.02 | ????50.53 |
Embodiment 2
This example explanation is phosphorous when use, during the catalyst B of the five-ring supersiliceous zeolite of iron and nickel, method provided by the invention is produced the situation of ethene and propylene.
With proportion be 0.873, boiling range is that 350～540 ℃ vacuum gas oil is a raw material, is that 620 ℃, agent-oil ratio are that 15: 1, water-oil ratio are that 0.4: 1, weight hourly space velocity are 150h in temperature of reaction
-1Operational condition under, on small fixed flowing bed-tion reacting device, carry out catalytic pyrolysis test, it the results are shown in table 2.
Comparative Examples 2
This example explanation when the contrast medium B of use phosphorated five-ring supersiliceous zeolite, with embodiment 2 identical operations conditions under the method that provides of prior art produce the situation of ethene and propylene, it the results are shown in table 2.
Table 2
| Catalyzer | Catalyst B | Contrast medium B |
| Product distributes, heavy % | ||
| Splitting gas | ????66.45 | ????65.66 |
| Wherein, ethene | ????16.02 | ????15.23 |
| Propylene | ????25.81 | ????24.35 |
| Butylene | ????12.02 | ????11.87 |
| Pyrolysis gasoline | ????15.88 | ????16.24 |
| Cracking light oil | ????5.42 | ????5.63 |
| Cracking heavy oil | ????4.47 | ????4.68 |
| Coke | ????7.78 | ????7.79 |
| Total gas olefins yield, heavy % | ????53.85 | ????53.85 |
Embodiment 3
This example illustrates that method provided by the invention is produced the situation of ethene and propylene when the catalyzer C of five-ring supersiliceous zeolite that uses phosphorous and iron and REHY zeolite.
With proportion be 0.873, boiling range is that 350～540 ℃ vacuum gas oil is a raw material, is that 550 ℃, agent-oil ratio are that 10: 1, water-oil ratio are that 0.3: 1, weight hourly space velocity are 250h in temperature of reaction
-1Operational condition under, on small fixed flowing bed-tion reacting device, carry out catalytic pyrolysis test, it the results are shown in table 3.
Comparative Examples 3
When this example explanation contains the contrast medium C of HZSM-5 zeolite and REHY zeolite when use, with embodiment 3 identical operations conditions under the method that provides of prior art produce the situation of ethene and propylene, it the results are shown in table 3.
Table 3
| Catalyzer | Catalyzer C | Contrast medium C |
| Product distributes, heavy % | ||
| Splitting gas | ????54.28 | ????51.83 |
| Wherein, ethene | ????4.96 | ????4.15 |
| Propylene | ????23.08 | ????21.37 |
| Butylene | ????14.38 | ????14.56 |
| Pyrolysis gasoline | ????28.59 | ????30.56 |
| Cracking light oil | ????7.16 | ????7.38 |
| Cracking heavy oil | ????5.45 | ????5.55 |
| Coke | ????4.52 | ????4.68 |
| Total gas olefins yield, heavy % | ????42.42 | ????40.08 |
From table 1,2 and 3 as can be seen, the productive rate of total gas olefins yield, the particularly ethene of method provided by the invention and propylene is all than Comparative Examples height.
Claims (15)
1. a catalytic thermocracking process of producing ethene and propylene is that the petroleum hydrocarbon raw material through preheating is sent in the riser reactor, contacts with the catalyzer that contains the five-ring supersiliceous zeolite of heat, and reacts under the catalytic pyrolysis condition; Reaction product isolated and reclaimable catalyst; Reaction product is sent into subsequent separation system and is carried out product separation, and reclaimable catalyst Returning reactor after stripping, regeneration recycles; Wherein, it is 0～70% clay, 5～99% inorganic oxide and 1～50% the zeolite of benchmark that described catalyzer contains with the catalyst weight, described zeolite is made up of the five-ring supersiliceous zeolite of 75～100 heavy % and the y-type zeolite of 0～25 heavy %, and the phosphorous and transition metal M of described five-ring supersiliceous zeolite, its anhydrous chemical expression is counted (0～0.3) Na with the quality of oxide compound
2O (0.3～5) Al
2O
3(1.0～10) P
2O
5(0.7～15) M
xO
y(0～10) RE
2O
3(70～98) SiO
2, wherein, M is selected from one or both transition metal among Fe, Co, Ni, Cu, Zn, Mo or the Mn, and x is the valency of oxygen, and y is the valency of transition metal.
2, according to the method for claim 1, it is characterized in that described clay is natural or synthetic, through or the various clays that are used as cracking catalyst carrier usually handled without various chemistry and/or physical method.
3,, it is characterized in that described clay is kaolin or halloysite according to the method for claim 2.
4,, it is characterized in that described inorganic oxide is selected from amorphous Si O according to the method for claim 1
2Al
2O
3, Al
2O
3And/or SiO
2
5, according to the method for claim 1, it is characterized in that the anhydrous chemical expression of described five-ring supersiliceous zeolite, count (0～0.2) Na with the quality of oxide compound
2O (0.9～5) Al
2O
3(1.5～7) P
2O
5(0.9～10) M
xO
y(0.5～10) RE
2O
3(82～92) SiO
2
6, according to the method for claim 1, it is characterized in that the anhydrous chemical expression of described five-ring supersiliceous zeolite, count (0～0.2) Na with the quality of oxide compound
2O (0.9～5) Al
2O
3(1.5～7) P
2O
5(0.9～10) M
xO
y(82～92) SiO
2
7,, it is characterized in that described M is selected from one or both among Fe, Co or the Ni according to the method for claim 1.
8,, it is characterized in that described M is Fe and/or Ni according to the method for claim 7.
9,, it is characterized in that described y-type zeolite contains or do not contain rare earth according to the method for claim 1.
10,, it is characterized in that described Y zeolite is REY or REHY according to the method for claim 9.
11. according to the method for claim 1, the product that it is characterized in that drawing from reactor is with cracking light oil, recycle stock, slurry oil and/or residual oil chilling.
12. according to the method for claim 1, catalyzer after it is characterized in that regenerating earlier through behind water vapor and/or the lighter hydrocarbons stripping again Returning reactor recycle.
13., it is characterized in that described lighter hydrocarbons are rich in methane according to the method for claim 12.
14., it is characterized in that described petroleum hydrocarbon raw material is atmospheric gas oil, vacuum gas oil or its mixture, and residual oil or crude oil according to the method for claim 1.
15., it is characterized in that the reaction conditions of described petroleum hydrocarbon raw material is as follows: the weight ratio 15～40 of 550～700 ℃ of temperature of reaction, 150～400 kPas of reaction pressures, catalyzer and stock oil: 1, the weight ratio 0.3～1: 1 of water vapor and stock oil according to the method for claim 1.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03147978 CN1234806C (en) | 2003-06-30 | 2003-06-30 | Catalytic pyrolysis process for producing petroleum hydrocarbon of ethylene and propylene |
| TW093117561A TWI259106B (en) | 2003-06-30 | 2004-06-17 | Catalyst conversion process for increasing yield of light olefins |
| US10/878,187 US7375256B2 (en) | 2003-06-30 | 2004-06-29 | Catalytic conversion process for producing light olefins with a high yield petroleum hydrocarbons |
| SG200403748A SG115708A1 (en) | 2003-06-30 | 2004-06-29 | A catalytic conversion process for producing light olefins with a high yield from petroleum hydrocarbons |
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|---|---|---|---|
| CN 03147978 CN1234806C (en) | 2003-06-30 | 2003-06-30 | Catalytic pyrolysis process for producing petroleum hydrocarbon of ethylene and propylene |
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| Publication Number | Publication Date |
|---|---|
| CN1566267A true CN1566267A (en) | 2005-01-19 |
| CN1234806C CN1234806C (en) | 2006-01-04 |
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| CN102274751A (en) * | 2010-06-11 | 2011-12-14 | 中国石油化工股份有限公司 | Steam stripping method for spent catalyst in process for preparing olefins by oxygenated chemicals |
| CN101213269B (en) * | 2005-06-29 | 2012-01-25 | 格雷斯公司 | Pentasil catalyst for light olefins in fluidized catalytic units |
| CN102453501A (en) * | 2010-10-26 | 2012-05-16 | 中国石油化工股份有限公司 | Hydrocarbon oil conversion method |
| CN102453502A (en) * | 2010-10-26 | 2012-05-16 | 中国石油化工股份有限公司 | hydrocarbon oil conversion process |
| CN104046376A (en) * | 2013-03-11 | 2014-09-17 | 中国石油化工股份有限公司 | Catalytic cracking method of lightweight hydrocarbon oil |
| US9486795B2 (en) | 2007-06-27 | 2016-11-08 | China Petroleum & Chemical Corporation | Catalytic cracking catalyst, its preparation and use |
| US9580664B2 (en) | 2010-09-27 | 2017-02-28 | China Petroleum & Chemical Corporation | Catalytic conversion method for improving product distribution |
-
2003
- 2003-06-30 CN CN 03147978 patent/CN1234806C/en not_active Expired - Lifetime
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005094992A1 (en) * | 2004-03-31 | 2005-10-13 | China Petroleum & Chemical Corporation | A catalyst containing zeolite for hydrocarbon converting and preparation thereof, and a hydrocarbon oil converting method using said catalyst |
| US7923399B2 (en) | 2004-03-31 | 2011-04-12 | China Petroleum & Chemical Corporation | Zeolite-containing hydrocarbon-converting catalyst, the preparation process thereof, and a process for converting hydrocarbon oils with the catalyst |
| CN101213269B (en) * | 2005-06-29 | 2012-01-25 | 格雷斯公司 | Pentasil catalyst for light olefins in fluidized catalytic units |
| US9486795B2 (en) | 2007-06-27 | 2016-11-08 | China Petroleum & Chemical Corporation | Catalytic cracking catalyst, its preparation and use |
| CN102274751A (en) * | 2010-06-11 | 2011-12-14 | 中国石油化工股份有限公司 | Steam stripping method for spent catalyst in process for preparing olefins by oxygenated chemicals |
| CN102274751B (en) * | 2010-06-11 | 2013-01-09 | 中国石油化工股份有限公司 | Steam stripping method for spent catalyst in process for preparing olefins by oxygenated chemicals |
| US9580664B2 (en) | 2010-09-27 | 2017-02-28 | China Petroleum & Chemical Corporation | Catalytic conversion method for improving product distribution |
| CN102453501A (en) * | 2010-10-26 | 2012-05-16 | 中国石油化工股份有限公司 | Hydrocarbon oil conversion method |
| CN102453502A (en) * | 2010-10-26 | 2012-05-16 | 中国石油化工股份有限公司 | hydrocarbon oil conversion process |
| CN102453502B (en) * | 2010-10-26 | 2014-01-15 | 中国石油化工股份有限公司 | Conversion method for hydrocarbon oil |
| CN104046376A (en) * | 2013-03-11 | 2014-09-17 | 中国石油化工股份有限公司 | Catalytic cracking method of lightweight hydrocarbon oil |
| CN104046376B (en) * | 2013-03-11 | 2016-03-02 | 中国石油化工股份有限公司 | Light hydrocarbon oil catalytic cracking method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1234806C (en) | 2006-01-04 |
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