CN1102634C - Catalyst for catalytic thermal cracking process to prepare lower olefine - Google Patents
Catalyst for catalytic thermal cracking process to prepare lower olefine Download PDFInfo
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- CN1102634C CN1102634C CN98120235A CN98120235A CN1102634C CN 1102634 C CN1102634 C CN 1102634C CN 98120235 A CN98120235 A CN 98120235A CN 98120235 A CN98120235 A CN 98120235A CN 1102634 C CN1102634 C CN 1102634C
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Abstract
The present invention relates to a catalyst for preparing low-carbon alkene by a catalytic thermal cracking process, which is prepared from the following ingredients (measured by the weight of the catalyst): 10 to 70% of clay soil, 5 to 85% of inorganic oxide and 1 to 50% of zeolite, wherein the zeolite is 0 to 25% of Y-type zeolite and 75 to 100% of silica-rich zeolite of a five-membered ring structure, which comprises phosphorus and aluminum, or magnesium, or calcium; the silica-rich zeolite is the zeolite of a ZSM-5 type, or a ZSM-8 type, or a ZSM-11 type, and contains 2 to 8% of phosphorus and 0.3 to 3% of aluminium, or magnesium, or calcium (measured by oxide); the ratio of silica to alumina is 15 to 60. The catalyst has excellent hydrothermal activity stability and the low-carbon alkene. In particular, the catalyst has a vinylic yield which can achieve the same low-carbon alkene yield as the thermal cracking process at the reaction temperature lower than that of the thermal cracking process.
Description
The invention relates to the catalyzer that is used for the petroleum hydrocarbon catalytic thermal cracking process to prepare lower olefine.Specifically, the invention relates to and be used for the petroleum hydrocarbon catalytic pyrolysis and produce ethene and propylene, pay the catalyzer that produces butylene.
The traditional method of producing ethene from petroleum hydrocarbon is to adopt pyrolysis in tubular furnace.The raw material that adopts is light petroleum hydrocarbons such as ethane, propane, butane, petroleum naphtha or solar oil.Also have and utilize heavy petroleum hydrocarbon heat carrier cracking legal system to get ethene.The thermal barrier that adopts is generally inert solids such as quartz sand, Jiao, coke.
Produce the method for low-carbon alkene many reported in literature are also arranged about petroleum hydrocarbon being carried out cracking or cracking with catalyzer, USP3,541,179, USP3,647,682, DD225,135 and SU1, what adopt in 214,726 is to be the metal load type catalyst of carrier with the oxide compound, and their carrier can be SiO
2Al
2O
3Or other oxide compound, the metal of institute's load is selected from IIB, VB, VIIB and VIIIB family element.When using this class catalyzer, because the dehydrogenation of loaded metal causes the also corresponding quickening of polymerization coking reaction when carrying out cracking reaction, so this type of catalyzer generally only is applicable to the light petroleum hydrocarbon of boiling point＜220 ℃.Have also that to adopt composite oxides be catalyzer, as USP3, the catalyzer of report is with ZrO in 725,495 and USP3,839,485
2And/or HfO
2Be main component, be aided with Al
2O
3, Cr
2O
3, MnO
2And/or Fe
2O
3And basic metal and alkaline earth metal oxide.Though can improve ethylene yield when adopting basic metal or alkaline earth metal oxide catalyzer but generate relatively large CO and CO simultaneously
2
Carry out the petroleum hydrocarbon cracking at the use solid acid catalyst and produce in the method for low-carbon alkene, as DD152,356A has used unformed SiO
2Al
2O
3Catalyzer with liquid hydrocarbon and various hydrocarbon-fraction, comprises that gasoline, kerosene, gas oil or decompression fraction oil are raw material, produces low-carbon alkene under 600～800 ℃ temperature of reaction, C
2 =～C
4 =Productive rate can reach 40～50 heavy % of raw material.JP60-222, having disclosed with HZSM-5 in 428 is active ingredient, Al
2O
3For the catalyzer of carrier carries out petroleum hydrocarbon cracked method, under 600～750 ℃ to C
5～C
25The paraffinic hydrocarbon raw material carry out catalytic cracking, C
2 =～C
4 =Productive rate be about 30 heavy %.USP3, having disclosed in 758,403 with ratio is that the catalyzer that 1: 10～3: 1 ZSM-5 zeolite and large pore zeolite (as X type, Y type) are active ingredient can make C when improving gasoline octane rating
3 =+ C
4 =The heavy % of gain in yield to 10 about.Having disclosed chemical constitution among the CN1069016A is 30～90%SiO
2, 20～70%Al
2O
3, 0.5～30% basic metal or alkaline earth metal oxide, 1～30% faujusite catalyzer under 650～900 ℃ with heavy hydrocarbon cracking, C
2 =Productive rate reaches 17～27%, C
2 =～C
4 =Productive rate reach 30～40%.US4 has used in 980,053 with HZSM-5 to active ingredient, the kaolin catalyzer as carrier, with the heavy hydrocarbon cracking, can obtain the C up to 40% in the product under 500～650 ℃
3 =+ C
4 =, but C
2 =Productive rate is lower.Use the acid molecular sieve catalyst that contains the cross-linked rectorite clay molecular sieve with layer structure and/or contain the rare-earth five-membered ring supersiliceous zeolite among the CN1083092A, under 680～780 ℃, the heavy hydrocarbon cracking can have been obtained the C of 23 heavy %
2 =The C of productive rate and 50 heavy %
2 =～C
4 =Productive rate.At USP5,380,690 and ZL CN93102783.7 in also to have disclosed a kind of be the catalyzer of active ingredient with y-type zeolite and the phosphorous and supersiliceous zeolite with five-membered ring structure rare earth, this catalyzer can improve the product gasoline octane rating when 500～600 ℃ of following cracking heavy oil fraction raw materials, improve C simultaneously
2 =～C
4 =Productive rate, and wherein with C
3 =And C
4 =Be main.
Purpose of the present invention promptly provides a kind of novel zeolite catalyst on the basis of above-mentioned prior art, this catalyzer can be that low temperature of reaction is issued to the productivity of low carbon olefin hydrocarbon with the same level of thermo-cracking than thermo-cracking.
Another object of the present invention provides a kind of above-mentioned Preparation of catalysts method.
Further aim of the present invention comprises that above-mentioned Application of Catalyst method all can learn from the specification sheets that comprises embodiment.
Contain a kind of in the catalyzer provided by the invention with the phosphorous-aluminium of ad hoc approach preparation or the five-membered ring structure high-silicon zeolite of phosphorus-magnesium or phosphorus-calcium.The existence of phosphorus can make this zeolite have higher hydro-thermal activity stability; The existence of aluminium or magnesium or calcium then can be regulated the acidity of zeolite, makes zeolite more help C
2 =Generation, this because of in the catalytic pyrolysis process on an acidic catalyst hydro carbons be to react by the carbonium ion reaction mechanism, its product low-carbon alkene is with C
3 =And C
4 =Be main, and C
2 =Be the product that the hydrocarbon pyrolysis free radical reaction generates, so an acidic catalyst and be unfavorable for C
2 =Generation.The zeolite that adopts among the present invention has been regulated the acidity of zeolite rightly, makes the existence of this zeolite catalyst both reduce the activation energy of petroleum hydrocarbon scission reaction, makes reaction improve C in the split product again being to carry out under the low temperature than thermo-cracking
2 =Productive rate.
Catalyzer provided by the invention has following composition (is benchmark in the catalyst weight): 10～70% clay, 5～85% inorganic oxide and 1～50% zeolite, said zeolite is y-type zeolite and the phosphorous and aluminium of 75～100 heavy % or the five-membered ring structure high-silicon zeolite of magnesium or calcium of 0～25 heavy %.
Wherein said clay can be natural or synthetic, through or without various chemistry and/or physical treatment, usually as the various clays of cracking catalyst carrier, as kaolin, halloysite etc.
Wherein said inorganic oxide is selected from amorphous silicon aluminium, aluminum oxide or silicon oxide.
Wherein said y-type zeolite can be that the content of rare earth that obtains after rare earth ion exchange is (with RE
2O
3Meter) being not less than the REY zeolite of 14 heavy %, also can be through various chemistry and/or physical method,, stabilization higher as the silica alumina ratio that obtains after the processing such as hydrothermal method, acidic treatment, aluminium-eliminating and silicon-replenishing method, silicon tetrachloride method type-Y high silicon zeolite.
The five-membered ring structure high-silicon zeolite of wherein said phosphorous and aluminium or magnesium or calcium be contain account for zeolite weight 2～8% phosphorus (with P
2O
5Meter) and 0.3～3% aluminium or ZSM-5, the ZSM-8 of magnesium or calcium (in oxide compound) or the supersiliceous zeolite of ZSM-11 type, its silica alumina ratio is preferably 15～60.Can also contain the nickel (in oxide compound) that accounts for zeolite weight 0.3～3% in the five-membered ring structure high-silicon zeolite of this phosphorous and aluminium or magnesium or calcium.
Preparation of catalysts method provided by the invention is as follows: the precursor of inorganic oxide is mixed with the clay predetermined amounts and with decationized Y sieve water it is mixed with the slurries that solid content is 10～50 heavy %, with mineral acid with its pH regulator and be maintained until 2～4, the zeolite that after leaving standstill aging 0～2 hour under 20～80 ℃, adds predetermined amount, homogeneous, spray shaping, washing are removed free Na
+, drying.
Wherein the precursor of said inorganic oxide is selected from aluminium colloidal sol, pseudo-boehmite, silicon sol and composition thereof, and silicon-aluminum sol or gel.
Said clay can be natural or synthetic, through or without various chemistry and/or physical treatment, usually as the various clays of cracking catalyst carrier, as kaolin, halloysite etc.
Said mineral acid is selected from hydrochloric acid, nitric acid, phosphoric acid or sulfuric acid.
Said zeolite is the mixture of the five-membered ring structure high-silicon zeolite of phosphorous and aluminium or magnesium or calcium or itself and y-type zeolite.Wherein the former be contain account for zeolite weight 2～8% phosphorus (with P
2O
5Meter) and 0.3～3% aluminium or ZSM-5, the ZSM-8 of magnesium or calcium (in oxide compound) or the supersiliceous zeolite of ZSM-11 type, its silica alumina ratio is preferably 15～60.Can also contain the nickel (in oxide compound) that accounts for zeolite weight 0.3～3% in this supersiliceous zeolite.This prepare zeolite method is as follows: with five-membered ring structure high-silicon zeolite according to 1～3: the solid weight ratio of 1 water joins in the aqueous solution that contains phosphorus and aluminium or magnesium or calcium cpd and mixes, dipping reaction 0.5～4 hour, 100～120 ℃ of dryings, 450～650 ℃ of roastings 1～4 hour.Nickel on the supersiliceous zeolite is to introduce by the compound of nickel is made aqueous solution dipping supersiliceous zeolite with the compound of phosphorus and aluminium or magnesium or calcium.Wherein said five-membered ring structure high-silicon zeolite is the supersiliceous zeolite of ZSM-5, ZSM-8 or ZSM-11 type, and its silica alumina ratio is preferably 15～60.The wherein said P contained compound aqueous solution is the aqueous solution of phosphoric acid preferably; The aqueous solution that contains aluminium or magnesium or calcium cpd can be the aqueous solution of nitrate, hydrochloride or the vitriol of these elements, the preferably aqueous solution of nitrate or hydrochloride.The compound of nickel can be nickelous nitrate, nickelous chloride or single nickel salt.
Y-type zeolite can be that the content of rare earth that obtains after rare earth ion exchange is (with RE
2O
3Meter) being not less than the REY zeolite of 14 heavy %, also can be through various chemistry and/or physical method, as hydrothermal method, acidic treatment, aluminium-eliminating and silicon-replenishing method, SiCl
4The silica alumina ratio that obtains after the processing such as method is higher, stabilization type-Y high silicon zeolite.
Catalyzer provided by the invention can be that low temperature of reaction is issued to the productivity of low carbon olefin hydrocarbon with the same level of thermo-cracking than thermo-cracking, this catalyzer has excellent hydrothermal activity stability and low-carbon alkene in the catalytic pyrolysis process, especially the productive rate of ethene.For example, this catalyzer 680 ℃, when agent-oil ratio 10, weight space velocity 10
-1Reaction conditions under, when being raw material with the vacuum gas oil, ethylene yield can reach 20 heavy % of stock oil, C
2 =～C
4 =The triolefin overall yield can reach 54 heavy %.
Following example will give further instruction to the present invention.
Employed phosphorous and aluminium or magnesium or calcium in the example, contain or being prepared as follows of nickeliferous five-membered ring structure high-silicon zeolite not: with commercially available ZSM-5 zeolite (Chang Ling oil-refining chemical factory catalyst plant product, silica alumina ratio 25.0) according to zeolite: ammonium nitrate: the weight ratio of deionized water=1: 1: 20 was 90 ℃ of following ion-exchanges 2 hours, filter washing back repeated exchanged and once obtain ammonium type ZSM-5, its Na
2The heavy % in O content≤0.15.With ammonium type zeolite with by phosphoric acid, deionized water and aluminum chloride or magnesium chloride or calcium chloride, add or do not add the solution that nickelous nitrate is mixed with and mix according to the solid weight ratio of 2: 1 water, stirred dipping 2 hours under the room temperature, 120 ℃ of oven dry, 550 ℃ of roastings 2 hours.What so make contains P
2O
54.9 heavy %, Al
2O
30.9 the ZSM-5 zeolite of heavy % note is made zeolite PAl-Z; What make contains P
2O
55.0 the ZSM-5 zeolite note of heavy %, MgO 1.4 heavy % is made zeolite PMg-Z; What make contains P
2O
54.9 the ZSM-5 zeolite note of heavy %, CaO 2.0 heavy % is made zeolite PCa-Z; What make contains P
2O
55.0 the ZSM-5 zeolite note of heavy %, MgO 1.4 heavy %, NiO 1.2 heavy % is made zeolite PMgNi-Z.
Example 1～3
The explanation of these examples is provided by the invention with the clay be matrix, pseudo-boehmite be binding agent single zeolite catalyst preparation and at little cracking performance on anti-.
With 34.36Kg decationized Y sieve water with 13.5Kg halloysite (Suzhou china clay company Industrial products, solid content 73 heavy %) making beating, add 13.5Kg pseudo-boehmite (Shandong Zibo aluminium manufacturer Industrial products again, solid content 64 weights) and 1.17 liter hydrochloric acid (concentration be 30 heavy %) stir, under 75 ℃, left standstill aging 1 hour, keep pH2～4, be cooled to 60 ℃, it is even to add the PAl-Z for preparing in advance, the PMg-Z and the PCa-Z zeolite thorough mixing that account for catalyst weight 15% respectively, spray drying forming, the flush away Na that dissociates
+, be drying to obtain catalyst sample A, B and C.
[contrast 1] is called five-ring supersiliceous zeolite (Zhou village, Shandong catalyst plant product, silica alumina ratio 30, the RE of the phosphorous and rare earth element of ZRP with commodity
2O
32.0 heavy %, P
2O
55.0 heavy %) be employed zeolite in the active ingredient replacement catalyzer of the present invention, make comparative sample 1 according to the proportioning and the method for example 1～3.
[contrast 2] is employed zeolite in the active ingredient replacement catalyzer of the present invention with HZSM-5 zeolite (Zhou village, Shandong catalyst plant product, silica alumina ratio ≮ 55), makes comparative sample 2 according to the proportioning and the method for example 1～3.
Table 1 has been listed the composition of above-mentioned each catalyst sample.Above-mentioned each catalyst sample through 800 ℃, 100% steam-treated after 4 hours the evaluation result on micro-reactor list in table 2.The micro anti-evaluation condition is: 520 ℃ of temperature of reaction, agent-oil ratio 3.2 is during weight space velocity 16
-1, catalyst sample loading amount 5.0 grams, the boiling range of raw materials used oil is 229～340 ℃, group composition is: paraffinic hydrocarbon 45.5 heavy %, naphthenic hydrocarbon 35.7 heavy %, aromatic hydrocarbons 18.2 heavy %, colloid 0.6 heavy %.
By table 2 data as can be known, activity of such catalysts good stability of the present invention: under same zeolite content and hydrothermal aging treatment condition, its activity exceeds about 14 units than comparative sample 1, exceeds about 19 units than comparative sample 2; Catalyzer C of the present invention
2 =Selectivity is good: C
2 =Productive rate is 2.5 times of comparative sample 1, is 4 times of comparative sample 2, C
2 =/ C
3 =Than about 3 times for comparative sample 1 or 2.
Example 4
The explanation of this example is provided by the invention to be matrix with the clay, and pseudo-boehmite is the preparation and the cracking performance thereof of the double zeolite catalyst of binding agent.
With 34.7Kg decationized Y sieve water the 15.3Kg halloysite is pulled an oar, add the 19.4Kg pseudo-boehmite again and 1.65 liter hydrochloric acid stir, under 75 ℃, left standstill aging 1 hour, keep pH2～4, be cooled to 60 ℃, add 3.0Kg (butt) PMg-Z zeolite, 0.8Kg (butt) commodity SRY zeolite by name (Chang Ling catalyst plant product, super steady type Y) and 5Kg decationized Y sieve water, homogeneous, spray drying forming, the flush away Na that dissociates
+, be drying to obtain catalyst sample D.
[contrast 3] is employed PMg-Z zeolite in the active ingredient replacement example 4 with the five-ring supersiliceous zeolite of the phosphorous and rare earth element of commodity ZRP by name, makes comparative sample 3 according to proportioning and the method for catalyst sample D.
Table 3 has been listed the composition of catalyst sample D and comparative sample 3.This two sample is listed in table 4 through 800 ℃, the micro-activity evaluation result of 100% steam-treated after 4 hours, and appreciation condition is with example 1～3.
The invention provides the C of catalyzer as can be known by data in the table
2 =Productive rate is 2.5 times of comparative sample, C
2 =/ C
3 =Than 3 times for comparative sample.
Example 5～7
The explanation of these examples is provided by the invention to be that matrix, pseudo-boehmite are the preparation of single zeolite catalyst of binding agent and the cracking performance on small fixed flowing bed thereof with the clay.
With 11.45Kg decationized Y sieve water the 3.39Kg halloysite is pulled an oar, add the 2.10Kg pseudo-boehmite again and 0.39 liter hydrochloric acid stirs, under 75 ℃, left standstill aging 1 hour, keep pH2～4, be cooled to 60 ℃, PAl-Z, the PMg-Z and the PCa-Z zeolite thorough mixing that add 0.675kg (butt) respectively are even, spray drying forming, the flush away Na that dissociates
+, be drying to obtain catalyst sample E, F and G.
[contrast 4] is employed zeolite in the active ingredient replacement catalyzer of the present invention with the five-ring supersiliceous zeolite of the phosphorous and rare earth element of commodity ZRP by name, makes comparative sample 4 according to the proportioning and the method for example 5～7.
Table 5 has been listed the composition of above-mentioned each catalyst sample.Catalyst sample E, F and G be through 800 ℃, 100% steam-treated 17 hours, comparative sample 4 through 760 ℃, 100% steam-treated after 10 hours on small fixed flowing bed evaluation result list in table 6.Appreciation condition is: 720 ℃ of temperature of reaction, agent-oil ratio 10, weight space velocity 10 time-1, water injection rate 80%, catalyst sample loading amount 180 grams, the boiling range of raw materials used oil is 346～546 ℃, the K value is 12.4, carbon residue 0.15 heavy %, density (20 ℃) 0.8730 gram per centimeter
3
The invention provides the C of catalyzer as can be known by data in the table
2 =Productive rate exceeds about 3～5 units than comparative sample.
Example 8～10
These example explanations are provided by the invention to be matrix with the clay, and alumino silica gel is the Preparation of catalysts of binding agent and the cracking performance on small fixed flowing bed thereof.
With the decationized Y sieve water of 43Kg and the water glass (SiO of 12Kg
2243 grams per liters, proportion 1.246) mix, add 1.9Kg halloysite and 0.75Kg (butt) PAl-Z zeolite again and fully pull an oar to evenly.In above-mentioned material, slowly add 3Kg alum liquor (Al
2O
3Content 93.5 grams per liters, proportion 1.287) and 5.6Kg decationized Y sieve water, control pH10～11 are stirred aging 30 minutes down, and then are slowly added the 2.6Kg alum liquor, and stirred aging 20 minutes down control pH4～5.To filter the gained filter cake and pull an oar with 15Kg decationized Y sieve water, spray drying forming, washing is drying to obtain catalyst sample H.
Replace PAl-Z to make catalyst sample I and J with PMg-Z and PCa-Z zeolite respectively.
[contrast 5] is employed zeolite in the active ingredient replacement catalyzer of the present invention with the five-ring supersiliceous zeolite of the phosphorous and rare earth element of commodity ZRP by name, makes comparative sample 5 according to the proportioning and the method for example 8～10.
Table 7 has been listed the composition of above-mentioned each catalyst sample.Above-mentioned each catalyst sample through 800 ℃, 100% steam-treated after 17 hours the evaluation result on small fixed flowing bed list in table 8, except that temperature of reaction is 700 ℃, all the other appreciation conditions are with example 5～7.
By data in the table as can be known, the gas yield that the invention provides catalyzer exceeds about 2～3 units, C than comparative sample
2 =Productive rate exceeds about 2 units, C
2 =～C
4 =Productive rate exceeds about 4 units.
Example 11～12
The explanation of these examples is provided by the invention is matrix with the clay, and pseudo-boehmite and aluminium colloidal sol are binding agent, the preparation of double zeolite catalyst and cracking performance thereof.
, add 1.82Kg pseudo-boehmite and 0.337 liter hydrochloric acid and stir the making beating of 3.26Kg halloysite with 10.7Kg decationized Y sieve water,, keep pH2～4, be cooled to 60 ℃, add 0.624Kg aluminium colloidal sol (Industrial products, Al 75 ℃ of static down wearing out 1 hour
2O
3Content is 0.2164 heavy %), stir, add 0.675Kg (butt) PMg-Z zeolite and 0.135Kg (butt) SRY zeolite and 3.68Kg decationized Y sieve water, homogeneous, spray drying forming, the flush away Na that dissociates
+, be drying to obtain catalyst sample K.
Replace PMg-Z to make catalyst sample L with the PMgNi-Z zeolite.
[contrast 6] is employed PMg-Z zeolite in the active ingredient replacement example 11 with the five-ring supersiliceous zeolite of the phosphorous and rare earth element of commodity ZRP by name, makes comparative sample 6 according to proportioning and the method for catalyst sample K.
Table 9 has been listed the composition of above-mentioned each catalyst sample.Above-mentioned each sample is through 800 ℃, 100% steam-treated after 17 hours the evaluation result on small fixed flowing bed list in table 10, except that temperature of reaction is 680 ℃, all the other appreciation conditions are with example 5～7.
The ethylene yield of catalyzer provided by the invention contrasts about 2～5 units of exceeding of sample, C as shown in Table 10
2 =～C
4 =Productive rate exceeds about 1.5～4.5 units.
Example 13
This example explanation is provided by the invention is matrix with the clay, and pseudo-boehmite and aluminium colloidal sol are binding agent, preparation and the cracking performance thereof of double zeolite catalyst on middle-scale device.
The catalyzer of this example prepares on medium-sized Preparation of Catalyst device.With 428Kg decationized Y sieve water the 132.4Kg halloysite is pulled an oar, add 72.8Kg pseudo-boehmite and 13.48 liter hydrochloric acid, stir, 75 ℃ of static down wearing out 1 hour, keep pH2～4, be cooled to 60 ℃, add 24.96Kg aluminium colloidal sol, stir, add 36Kg (butt) PMg-Z zeolite and 63Kg (butt) SRY and 147Kg decationized Y sieve water again, homogeneous, spray drying forming, the flush away Na that dissociates
+, be drying to obtain catalyst sample M.Table 11 is formed for this catalyst sample.
Through 790 ℃, 100% steam-treated is after 27 hours on medium-sized hydrothermal treatment device for this catalyst sample, and evaluation result is listed in table 12 on medium-sized riser tube catalytic pyrolysis device.Riser tube inner catalyst reserve is 55Kg.Raw materials used oil nature is as follows: density (20 ℃) 0.8826 gram per centimeter
3, carbon residue 2.9 heavy %, 46 ℃ at zero pour, stable hydrocarbon 59.8 heavy %, aromatic hydrocarbons 26.4 heavy %, colloid 13.2 heavy %, bituminous matter 0.6 heavy %.
Table 1
Table 2
Table 3
| Catalyst sample | D | Contrast 3 |
| Kaolin, heavy % Al 2O 3Heavy % zeolite, heavy % PMg-Z ZRP SRY | 53.0 28.0 15.0 4.0 | 53.0 28.0 15.0 4.0 |
Table 4
Table 5
| Catalyst sample | E | F | G | Contrast 4 |
| Kaolin, heavy % Al 2O 3Heavy % zeolite, heavy % PAl-Z PMg-Z PCa-Z ZRP | 55 30 15 | 55 30 15 | 55 30 15 | 55 30 15 |
Table 6
Table 7
| Catalyst sample | H | I | J | Contrast 5 |
| Kaolin, heavy % SiO 2·Al 2O 3Heavy % zeolite, heavy % PAl-Z PMg-Z PCa-Z ZRP | 28 57 15 | 28 57 15 | 28 57 15 | 28 57 15 |
Table 8
Table 9
| Catalyst sample | K | L | Contrast sample 6 |
| Kaolin, heavy % Al 2O 3Heavy % zeolite, heavy % PMg-Z PMgNi-Z ZRP SRY | 53 29 15 3 | 53 29 15 3 | 53 29 15 3 |
Table 10
Table 11
| Catalyst sample | M |
| Kaolin, heavy % Al 2O 3, heavy % zeolite, heavy % PMg-Z SRY | 51.5 25 20 3.5 |
Table 12
Claims (10)
1. catalyzer that is used for catalytic thermal cracking process to prepare lower olefine, it is characterized in that having following composition: account for the clay of catalyst weight 10-70%, the inorganic oxide of 5-85% and the zeolite of 1-50%, its mesolite is y-type zeolite and the phosphorous and aluminium of 75-100% or the five-membered ring structure high-silicon zeolite of magnesium or calcium of 0-25%, this supersiliceous zeolite is to contain the phosphorus that accounts for zeolite weight 2-8% and aluminium or ZSM-5, the ZSM-8 of magnesium or calcium (in oxide compound) or the supersiliceous zeolite of ZSM-11 type of 0.3-3%, and its silica alumina ratio is 15-60.
2. according to the described catalyzer of claim 1, it is characterized in that clay wherein is selected from kaolin or halloysite.
3. according to the described catalyzer of claim 1, it is characterized in that inorganic oxide wherein is selected from amorphous silicon aluminium, aluminum oxide or silicon oxide.
4. according to the described catalyzer of claim 1, it is characterized in that y-type zeolite wherein is selected from content of rare earth (with RE
2O
3Meter) be not less than the REY of 14 heavy % or the silica alumina ratio that obtains after chemistry and/or physical method are handled is higher, stabilization high-silicon Y-Zeolite.
5. according to the described catalyzer of claim 1, it is characterized in that wherein phosphorous and aluminium or the five-ring supersiliceous zeolite of magnesium or calcium in also can contain the nickel (in oxide compound) that accounts for zeolite weight 0.3-3%.
6. claim 1 Preparation of catalysts method, it is characterized in that: the precursor of inorganic oxide being mixed with clay and make solid content is the slurries that 10-50 weighs %, with mineral acid with its pH regulator and be maintained until 2-4, after leaving standstill aging 0-2 hour under 20-80 ℃, add the zeolite homogeneous, spray shaping, washing, drying; Wherein said zeolite is the mixture of the five-membered ring structure high-silicon zeolite of phosphorous and aluminium or magnesium or calcium or itself and y-type zeolite; Five-membered ring structure high-silicon zeolite wherein is to contain the phosphorus that accounts for zeolite weight 2-8% and aluminium or ZSM-5, the ZSM-8 of magnesium or calcium (in oxide compound) or the zeolite of ZSM-11 type of 0.3-3%.
7. according to the described preparation method of claim 6, it is characterized in that inorganic oxide precursor wherein is selected from aluminium colloidal sol, pseudo-boehmite, silicon sol and composition thereof, and silicon-aluminum sol or gel.
8. according to the described preparation method of claim 6, it is characterized in that to contain in the five-membered ring structure high-silicon zeolite wherein the nickel (in oxide compound) that accounts for zeolite weight 0.3-3%.
9. according to the described preparation method of claim 6, it is characterized in that wherein the phosphorous and aluminium or the preparation method of the five-membered ring structure high-silicon zeolite of magnesium or calcium are as follows: with ZSM-5, ZSM-8 or ZSM-11 type zeolite according to 1-3: the solid weight ratio of 1 water joined in the aqueous solution that contains phosphorus and aluminium or magnesium or calcium cpd dipping 0.5-4 hour, 100-120 ℃ of drying, 450-650 ℃ roasting 1-4 hour.
10. according to the described preparation method of claim 9, it is characterized in that the P contained compound aqueous solution wherein is phosphate aqueous solution, the aqueous solution that contains aluminium or magnesium or calcium cpd is selected from their nitrate, hydrochloride or sulfate solution.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98120235A CN1102634C (en) | 1997-10-15 | 1998-10-06 | Catalyst for catalytic thermal cracking process to prepare lower olefine |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97119012.7 | 1997-10-15 | ||
| CN97119012 | 1997-10-15 | ||
| CN98120235A CN1102634C (en) | 1997-10-15 | 1998-10-06 | Catalyst for catalytic thermal cracking process to prepare lower olefine |
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| CN1222558A CN1222558A (en) | 1999-07-14 |
| CN1102634C true CN1102634C (en) | 2003-03-05 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98120235A Expired - Lifetime CN1102634C (en) | 1997-10-15 | 1998-10-06 | Catalyst for catalytic thermal cracking process to prepare lower olefine |
Country Status (1)
| Country | Link |
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| CN (1) | CN1102634C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1303044C (en) * | 2004-05-28 | 2007-03-07 | 中国石油化工股份有限公司 | Catalyst for olefin cracking preparation of propylene and ethylene |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100497530C (en) * | 2004-12-28 | 2009-06-10 | 中国石油化工股份有限公司 | Method for cracking hydrocarbon oil |
| CN101134172B (en) | 2006-08-31 | 2010-10-27 | 中国石油化工股份有限公司 | Hydrocarbons conversion catalyzer |
| CN101134913B (en) | 2006-08-31 | 2011-05-18 | 中国石油化工股份有限公司 | Hydrocarbons catalytic conversion method |
| CN101332433B (en) | 2007-06-27 | 2011-07-20 | 中国石油化工股份有限公司 | Catalytic cracking catalyst, preparation method and use thereof |
| CN101455979B (en) * | 2007-12-13 | 2012-12-12 | 中国石油化工股份有限公司 | Catalytic cracking catalyst with dehydrogenation activity |
| CN102019200B (en) * | 2010-04-13 | 2013-01-16 | 卓润生 | High-activity catalytic pyrolysis catalyst and preparation method thereof |
| CN102794195B (en) * | 2012-08-28 | 2014-08-27 | 丁泳 | Catalyst suitable for enhancing gasoline octane number of fuel and lowering olefin content and application thereof |
| CN106582889B (en) * | 2015-10-15 | 2019-11-08 | 中国石油化工股份有限公司 | Highly resistance nitrogen carrier of hydrocracking catalyst and preparation method thereof |
| RU2710856C1 (en) * | 2019-09-16 | 2020-01-14 | Акционерное общество "Газпромнефть - Омский НПЗ" (АО "Газпромнефть-ОНПЗ") | Method for joint oil fraction cracking |
| CN113070095B (en) * | 2021-04-09 | 2023-03-28 | 陕西延长石油（集团）有限责任公司 | Catalyst for preparing low-carbon olefin by catalytic cracking of light hydrocarbon and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5302567A (en) * | 1991-11-04 | 1994-04-12 | W. R. Grace & Co.-Conn. | Zeolite octane additive |
| CN1093101A (en) * | 1993-03-29 | 1994-10-05 | 中国石油化工总公司 | Produce the catalyst for cracking of low-carbon alkene |
| CN1117518A (en) * | 1994-08-22 | 1996-02-28 | 中国石油化工总公司 | Double zeolite catalyst for prepn. of low carbon olefine |
-
1998
- 1998-10-06 CN CN98120235A patent/CN1102634C/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5302567A (en) * | 1991-11-04 | 1994-04-12 | W. R. Grace & Co.-Conn. | Zeolite octane additive |
| CN1093101A (en) * | 1993-03-29 | 1994-10-05 | 中国石油化工总公司 | Produce the catalyst for cracking of low-carbon alkene |
| CN1117518A (en) * | 1994-08-22 | 1996-02-28 | 中国石油化工总公司 | Double zeolite catalyst for prepn. of low carbon olefine |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1303044C (en) * | 2004-05-28 | 2007-03-07 | 中国石油化工股份有限公司 | Catalyst for olefin cracking preparation of propylene and ethylene |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1222558A (en) | 1999-07-14 |
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