CN1053918C - Double zeolite catalyst for prepn. of low carbon olefine - Google Patents
Double zeolite catalyst for prepn. of low carbon olefine Download PDFInfo
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- CN1053918C CN1053918C CN94114963A CN94114963A CN1053918C CN 1053918 C CN1053918 C CN 1053918C CN 94114963 A CN94114963 A CN 94114963A CN 94114963 A CN94114963 A CN 94114963A CN 1053918 C CN1053918 C CN 1053918C
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Abstract
The present invention relates to a catalyst for preparing low carbon olefine by converting petroleum hydrocarbon. The present invention is composed of 0 to 70 wt% of clay, 5 to 90 wt% of inorganic oxide, and 10 to 40 wt% of zeolite, wherein the zeolite is composed of 25 to 75 wt% of five-element ring high silicon zeolite containing phosphorus and rare earth, and 25 to 75 wt% of high silicon Y-type zeolite or Y-type zeolite containing rare earth. The catalyst has the characteristics of high hydrothermal activity stability, high conversion rate and high yield of low carbon olefine, particularly propene, isobutene and isoamylene in a product.
Description
The present invention relates to the petroleum hydrocarbon cracking and produce the catalyzer of low-carbon alkene, more particularly, the present invention relates to the petroleum hydrocarbon cracking and produce the particularly catalyzer that contains crystal silicon-aluminate zeolite of iso-butylene and isopentene of ethene, propylene, butylene and amylene.
Produce low-carbon alkenes such as ethene, propylene, butylene from petroleum hydrocarbon, generally adopting with Sweet natural gas, petroleum naphtha or solar oil is the pyrolysis in tubular furnace of raw material; With the heavy hydrocarbon is the heat carrier cracking of raw material; Or be the catalysis conversion method of raw material with the low-carbon alcohol.And conventional catalytic cracking unit also by-product low-carbon alkene when producing gasoline and diesel oil, but its output only accounts for below the 15 heavy % of stock oil.
Once having many patents to introduce the employing appropriate catalyst, under certain reaction type formula and operational condition, is the method that raw material is produced low-carbon alkene with the petroleum hydrocarbon.For example, USP 3,541, introduced aluminum oxide, silicon oxide or other oxide compound of working load IIB, VB, VIIB and VIII family element in 179, USP3,647,682, DD225,135 and SU1,214,726 and produced low-carbon alkene as catalyzer.But because the metal of these loads has dehydrogenation functionality, in the cracking reaction process, quickened condensation green coke process, so this class catalyzer only is applicable to the lightweight material of processing boiling range below 220 ℃.
At SU523, introduced use potassium vanadate, potassium stannate or potassium niobate in 133, SU487,927 and SU410,073 and gasoline has been carried out cracking as catalyzer, obtained the low-carbon alkene of about 56 heavy %, its ethylene yield reaches 36.5 heavy %, and productivity of propylene reaches 12.5 heavy %; At DD152, introduced use amorphous silicon Al catalysts in 356, in fixed bed or moving-burden bed reactor petroleum hydrocarbon (comprising gasoline, diesel oil, gas oil or decompression fraction oil) has been carried out cracking, its temperature of reaction is 600～800 ℃, reaction times is 0.3～0.7 second, C
2～
4Olefins yield is 40～55%; At JP60-222, introduced use ZSM-5 catalyzer in 428, with C
5～C
25Paraffinic hydrocarbon is a raw material, and its temperature of reaction is 600～750 ℃, and the charging air speed is 20～300 o'clock
-1, C
2～
4Olefins yield reaches about 30%.The main drawback of aforesaid method is the temperature height of scission reaction, and raw materials used boiling spread is narrow.
It is matrix with 0～70 heavy % clay and 5～99 heavy % inorganic oxides that the applicant once disclosed a kind of in CN1043520A, the ZSM-5 of 1～50 heavy % and the mixture of Y zeolite are the catalyst for cracking of active ingredient, and this catalyzer is only applicable to produce propylene and butylene by the stock oil of multiple boiling range scope.The applicant then discloses a kind of catalyzer that is active ingredient with ZSM-5, REY and three kinds of zeolites of high silicon Y in CN1072201A, this catalyzer is used for producing propylene, butylene and high-quality gasoline by the stock oil of various boiling range scopes.The applicant also discloses another kind of with the catalyzer that to contain rare-earth five-membered ring supersiliceous zeolite, REY and three kinds of zeolites of high silicon Y be active ingredient in CN1085825A, and this catalyzer is used for the stock oil of various boiling range scopes equally and produces propylene, butylene and high-quality gasoline.
In recent years, abroad some companies are all managing to make FCC apparatus volume increase iso-butylene and isopentene to produce gasoline blend component oxycompound by changing catalyzer.Using boiling range as Grace company is that 215～556 ℃, K value are 11.51 nitrogen-containing material, when 521 ℃ temperature of reaction, transformation efficiency are 68 weight %, use the RFG catalyzer, productivity of propylene is 6.3～6.8 heavy %, the iso-butylene productive rate is 3.8～4.0 heavy %, and the isopentene productive rate is 4.7～5.1 heavy %; When catalyzer changes into when being active ingredient with 90%USY+10%ZSM-5, under identical temperature of reaction and transformation efficiency, productivity of propylene is 8.7 heavy %, and the iso-butylene productive rate is 3.6 heavy %, the isopentene productive rate be 3.9 heavy % (NPRAAM-91-34, AM-92-43).And for example Engelhard company uses middle-eastern crude gas oil to be raw material, and catalyzer is Isoplus-2000, and when transformation efficiency was 70 weight %, the iso-butylene productive rate was 3.3 heavy %, and the isopentene productive rate is 4.5 heavy %; When employing was the catalyzer of active ingredient with the REUSY zeolite, the iso-butylene productive rate was 0.58 heavy % under identical transformation efficiency, and the isopentene productive rate is 2.6 heavy % (NPRA AM-92-45).For another example Uop Inc. with the API value be 26.24, the K value is that 11.87 mixing VGO is when being raw material, USY with low content of rare earth is the activity of such catalysts component, when 549 ℃ temperature of reaction, transformation efficiency were 82.9 weight %, the iso-butylene productive rate was 2.08 heavy %, and the isopentene productive rate is 2.43 heavy %; When being the activity of such catalysts component with the USY of low content of rare earth and 5% ZSM-5, when 527 ℃ temperature of reaction, transformation efficiency were 80.8 heavy %, the iso-butylene productive rate was 2.36 heavy %, and the isopentene productive rate is 2.56 weight % (NPRA AM-92-26).Also having Mobil company in addition is catalyzer (ACSPreprints with the faujusite that contains rare earth and the mixture of ZSM-5 zeolite, 35 (4), 678～683), Hispanic Institute for Research and Technology is catalyzer (Appl.Catal. with the β zeolite, 82 (1), 37～50,1992) try hard to improve the productive rate of different propylene and iso-butylene in the FCC apparatus.
The purpose of this invention is to provide a kind of new catalyst, in the hope of obtaining the productive rate of low-carbon alkene, particularly propylene, iso-butylene and isopentene higher in the product.
Catalyzer provided by the invention has following composition: the zeolite of the inorganic oxide of the clay of 0～70 heavy %, 5～90 heavy % and 10～40 heavy %, said zeolite are the type-Y high silicon zeolite of the five-ring supersiliceous zeolite of phosphorous and rare earth of 25～75 heavy % and 25～75 weight % or the mixture that contains the y-type zeolite of rare earth.
Clay in this catalyzer 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.
Inorganic oxide in this catalyzer is selected from amorphous Si O
2Al
2O
3, Al
2O
3Or/and SiO
2
Type-Y high silicon zeolite in this catalyzer is with chemistry and/or physical method, as hydrothermal method, acidic treatment, aluminium-eliminating and silicon-replenishing method, SiCl
4That obtain after the processing such as method, that contain or do not contain rare earth, stabilization type-Y high silicon zeolite.
The y-type zeolite that contains rare earth in this catalyzer is selected from Rare Earth Y (REY), rare earth hydrogen Y (REHY).
The five-ring supersiliceous zeolite of the phosphorous and rare earth in this catalyzer be with aluminum phosphate handle the five-ring supersiliceous zeolite that contains rare earth, phosphorous in this zeolite (with P
2O
5Meter) 2～20 heavy %, best 2～10 heavy % contain rare earth (with RE
2O
3Meter) 2～10 heavy %.
The five-ring supersiliceous zeolite (trade names ZRP) that contains rare earth be the applicant at USP5, the zeolite disclosed in 232,675, it has the x-ray diffraction spectra of ZSM-5 zeolite family, its anhydrous chemical constitution expression formula is: 0.01～0.30RE
2O
30.4～1.0NaOAl
2O
320～60SiO
2, the used faujasite seeds that contains rare earth when synthetic of the rare earth in this composition, the duct of this zeolite is narrow than the ZSM-5 zeolite, it is 2～4 times of ZSM-5 zeolite to the ratio of the adsorptive capacity of normal hexane and hexanaphthene.This zeolite is to be raw material with water glass, aluminum phosphate, mineral acid, is crystal seed with REY or REHY zeolite, makes in 12～60 hours at 130～200 ℃ of following crystallizations.
The method of handling the ZRP zeolite with aluminum phosphate is as follows: zeolite is exchanged processing in advance with ammonium ion make its content (with Na
2O meter) reduces to and be not more than 0.1 heavy %, will consist of Al
2O
3: P
2O
5=1: 1～3 aluminum phosphate colloid is according to P
2O
5: weight ratio and this zeolite of zeolite (butt)=1: 5～99 mix, and have roasting down 0.5～6 hour in 300～600 ℃, 10～100% water vapors.
Catalyzer method for making provided by the invention is as follows: with the precursor of inorganic oxide, as aluminium colloidal sol, pseudo-boehmite, silicon sol or its mixture and silicon-aluminum sol or gel, mix by preset blending ratio with clay, and it is mixed with the slurries that solid content is 10～50 heavy % with decationized Y sieve water, stir, use mineral acid, example hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid transfer to 2～4 with slurries PH, keep this pH value, the zeolite that after leaving standstill aging 0～2 hour under 20～80 ℃, adds predetermined amount, homogeneous, spraying drying, the flush away free sodium ion, drying.
Catalyzer provided by the invention has hydro-thermal activity stability height, transformation efficiency height, heavy oil conversion rate height and C when being used for catalytic pyrolysis
2 -～C
5 -, particularly iso-butylene and the high characteristics of isopentene productive rate.On the small fixed flowing bed device, be raw material for example with the paraffinic base wax oil, catalyst sample through 790 ℃, 100% steam-treated after 14 hours 530 ℃, when agent-oil ratio 6, weight space velocity 10
-1Condition under carry out cracking performance when evaluation, C when transformation efficiency is 83～88 heavy %
2 -～C
5 -And iC
4 -+ iC
5 -Productive rate can reach 35.6～41.5% and 7.8～9.8% of raw material weight respectively.
Following example will give further instruction to the present invention.
Being prepared as follows of five-ring supersiliceous zeolite (following brief note is P-ZRP) of used phosphorous and rare earth in the example: get 100 gram (butt) ZRP zeolite (Zhou village, Shandong catalyst plant product, SiO
2/ Al
2O
330, RE
2O
32.0%), according to zeolite (butt): ammonium sulfate: the weight ratio of decationized Y sieve water=100: 25: 2000 exchanges after the filtration 1 time 90 ℃ of following ion-exchanges 1 hour again.Atomic absorption spectrum records in this zeolite sodium content (with Na
2The O meter) be 0.04%.With 13.8 gram pseudo-boehmite (Shandong Aluminum Plant's product, Al
2O
395%, solid content 30%), 9.0 gram industrial phosphoric acids (content 85%) and 200 gram decationized Y sieve water mix the back add above-mentioned ammonium exchange zeolite in, stir, 110 ℃ of dry backs promptly got phosphorus content (with P in aging 4 hours in 800 ℃, 100% water vapour atmosphere
2O
5Meter) is the five-ring supersiliceous zeolite P-ZRP of 5% phosphorous and rare earth.
The salient features of the used stock oil of evaluate catalysts sees Table 1 in the example.
Table 1
| The intermediate base wax oil | The paraffinic base wax oil | |
| Density (20 ℃), gram per centimeter 3The electric furnace process carbon residue, heavy % alkali nitrogen, ppm boiling range, ℃ UOP K value | 0.8808 0.10 537 256～545 12.0 | 0.8560 0.69 420 319～504 — |
Example 1
Provided by the invention is that active ingredient, clay are that matrix, pseudo-boehmite are the Preparation of Catalyst and the cracking performance thereof of binding agent with P-ZRP with the high silicon Y that contains rare earth.
With 394 kilograms of decationized Y sieve water with 123.3 kilograms of halloysites (Suzhou china clay company Industrial products, solid content 0.73) making beating, add 187.5 kilograms of pseudo-boehmites (Shandong Aluminum Plant's Industrial products, solid content 0.32) again, its pH is transferred to 2～4 with hydrochloric acid, stir, under 75 ℃, left standstill aging 1 hour, and kept pH2～4, cool the temperature to below 60 ℃, add the P-ZRP and SRNY (Chang Ling catalyst plant product, the lattice constant a that contain 50 kilograms (butts)
o=2.440～2.442 nanometers, RE
2O
3The decationized Y sieve aqueous slurry of zeolite mixture 5～7%) stirs, spray drying forming, the flush away Na that dissociates
+, be drying to obtain catalyst sample A.
Table 2 has been listed the composition of this catalyzer.For the purpose of contrast, listed file names with in the table 2 according to the method described in the example 1 of CN1043520A, be the catalyzer (note is done contrast 1) that active ingredient makes with ZSM-5 and SRNY zeolite mixture.
On the small fixed flowing bed device, be that raw material is estimated above-mentioned catalyst sample with the paraffinic base wax oil, temperature of reaction is 530 ℃, agent-oil ratio 6 is during weight space velocity 10
1, through 790 ℃, 100% steam-treated 14 hours, loading amount was 180 grams to catalyst sample in advance, evaluation result sees Table 3.
Table 2
| Catalyzer | A | Contrast 1 |
| Catalyzer is formed, and heavy % kaolin alumina zeolites is P-ZRP SRNY ZSM-5 wherein | 45.0 30.0 25.0 40.0 60.0 0.0 | 54.0 22.0 23.0 0.0 53.0 47.0 |
Table 3
| Catalyzer | A | Contrast 1 |
| Transformation efficiency, heavy % product distributes, heavy % reacted gas gasoline (C 5～221 ℃) diesel oil (221～330 ℃) heavy oil (＞330 ℃) coke olefins yield wherein, heavy % C 2 - C 3 -Total C 4 -Different C 4 -Total C 5 -Different C 5 - | 87.15 45.18 37.53 8.65 4.20 4.44 2.78 15.44 12.88 5.07 5.85 3.80 | 85.28 39.46 40.91 8.10 6.70 4.91 2.59 14.44 11.15 4.14 5.24 3.10 |
| C 2 -～C 5 -, heavy % iC 4 -+iC 5 -, heavy % | 36.95 8.87 | 33.42 7.24 |
Example 2
Provided by the invention is that active ingredient, clay are that matrix, pseudo-boehmite are the Preparation of catalysts and the cracking performance thereof of binding agent with P-ZRP and high silicon Y.
According to each proportioning raw materials and the preparation method of example 1, prepare that (Zhou village, Shandong catalyst plant product, the hydrothermal method dealuminzation makes, SiO with P-ZRP and DASY
2/ Al
2O
38～9) zeolite mixture is the catalyst sample B of active ingredient.
Listed the composition of this catalyzer in the table 4.For the purpose of contrast, listed file names with the catalytic cracking catalyst (note is done contrast 2) of the interpolation auxiliary agent of industrial use in the table 4.The active ingredient of the cracking catalyst in this contrast medium 2 is the DASY zeolite, and the active ingredient of auxiliary agent is the ZSM-5 zeolite, and catalyzer and auxiliary agent all are that matrix, pseudo-boehmite are binding agent with the clay.
On the small fixed flowing bed device above-mentioned catalyst sample is estimated, appreciation condition is with example 1, and evaluation result sees Table 5.
Table 4
| Catalyzer | B | Contrast 2 |
| Catalyzer is formed, and heavy % kaolin alumina zeolites is P-ZRP DASY ZSM-5 wherein | 45.0 30.0 25.0 40.0 60.0 0.0 | 45.0 30.0 25.0 0.0 60.0 40.0 |
Table 5
| Catalyzer | B | Contrast 2 |
| Transformation efficiency, heavy % product distributes, heavy % reacted gas gasoline (C 5～221 ℃) diesel oil (221～330 ℃) heavy oil (＞330 ℃) coke olefins yield wherein, heavy % C 2 - C 3 -Total C 4 -Different C 4 -Total C 5 -Different C 5 - | 88.62 46.25 37.24 7.62 3.76 5.13 3.09 15.11 12.32 4.93 5.60 3.64 | 83.62 37.70 41.84 9.27 7.11 4.08 1.51 13.18 11.85 4.66 5.39 3.66 |
| C 2 -～C 5 -, heavy % iC 4 -+iC 5 -, heavy % | 36.12 8.57 | 31.93 8.32 |
Example 3
Provided by the invention is that active ingredient, clay are that matrix, pseudo-boehmite are the Preparation of catalysts and the cracking performance thereof of binding agent with P-ZRP and REY.
According to the preparation method of example 1, with 190 kilograms of decationized Y sieve water, 67.1 kilograms of halloysites, 94 kilograms of pseudo-boehmites, 21 kilograms of P-ZRP and REY (Zhou village, Shandong catalyst plant product, SiO
2/ Al
2O
3≮ 4.7, RE
2O
3≮ 17%) zeolite mixture is prepared catalyst sample C.
Listed the composition of this catalyzer in the table 6.For the purpose of contrast, contrast 1 and contrast 2 have been listed file names with in the table 6.
On the small fixed flowing bed device above-mentioned catalyst sample is estimated, appreciation condition is with example 1, and evaluation result sees Table 7.
Table 6
| Catalyzer | C | Contrast 1 | Contrast 2 |
| Catalyst forms, and heavy % kaolin alumina zeolites is P-ZRP REY SRNY DASY ZSM-5 wherein | 49.0 30.0 21.0 71.4 28.6 0.0 0.0 0.0 | 54.0 22.0 23.0 0.0 0.0 53.0 0.0 47.0 | 45.0 30.0 25.0 0.0 0.0 0.0 60.0 40.0 |
Table 7
| Catalyzer | C | Contrast 1 | Contrast 2 |
| Transformation efficiency, heavy % product distributes, heavy % reacted gas gasoline (C 5～221 ℃) diesel oil (221～330 ℃) heavy oil (＞330 ℃) coke olefins yield wherein, heavy % C 2 - C 3 -Total C 4 -Different C 4 -Total C 5 -Different C 5 - | 86.54 48.18 33.13 8.34 5.12 5.23 4.02 17.72 13.40 5.45 6.36 4.34 | 85.28 39.46 40.91 8.10 6.70 4.91 2.59 14.44 11.15 4.14 5.24 3.10 | 83.62 37.70 41.84 9.27 7.11 4.08 1.51 13.18 11.85 4.66 5.39 3.66 |
| C 2 -～C 5 -, heavy % iC 4 -+iC 5 -, heavy % | 41.50 9.79 | 33.42 7.24 | 31.93 8.32 |
Example 4～6
Provided by the invention is that active ingredient, clay are that matrix, pseudo-boehmite are the Preparation of catalysts and the cracking performance thereof of binding agent with P-ZRP and high silicon Y.
According to the preparation method of example 1, (Zhou village, Shandong catalyst plant product, the dealumination complement silicon method makes, SiO with P-ZRP and RSY
2/ Al
2O
3≮ 11) zeolite mixture is that active ingredient is prepared catalyst sample D, E, F.
Each raw material consumption and catalyzer composition in the above-mentioned Preparation of Catalyst have been listed in the table 8.For the purpose of contrast, listed file names with the catalyzer (note is done contrast 3) described in the example 3 of CN1043520A in the table 8.Contrast active ingredient USY in 3 samples and be through twice ammonium sulfate exchange-roasting and the SiO that makes repeatedly
2/ Al
2O
3≮ 10 high silicon Y.
Be that raw material is estimated above-mentioned catalyst sample with the intermediate base wax oil on the small fixed flowing bed device, temperature of reaction is 520 ℃, agent-oil ratio 8, and other appreciation condition is with example 1, and evaluation result sees Table 9.
Table 8
| Catalyzer | D | E | F | Contrast 3 |
| The raw material consumption, kilogram decationized Y sieve water halloysite pseudo-boehmite zeolite mixture | 22.0 6.17 9.38 2.50 | 22.0 5.75 8.76 3.00 | 21.0 5.48 7.82 3.50 | |
| Catalyst forms, and heavy % kaolin alumina zeolites is P-ZRP RSY ZSM-5 USY wherein | 45.0 30.0 25.0 60.0 40.0 0.0 0.0 | 42.0 28.0 30.0 50.0 50.0 0.0 0.0 | 40.0 25.0 35.0 57.1 42.9 0.0 0.0 | 54.0 27.0 19.0 0.0 0.0 90.0 10.0 |
Table 9
| Catalyzer | D | E | F | Contrast 3 |
| Transformation efficiency, heavy % product distributes, heavy % reacted gas gasoline (C 5～221 ℃) diesel oil (221～330 ℃) heavy oil (＞330 ℃) coke olefins yield wherein, heavy % C 2 - C 3 -Total C 4 -Different C 4 -Total C 5 -Different C 5 - | 72.83 31.54 35.12 15.28 11.89 6.17 1.50 10.43 8.67 3.37 3.91 2.74 | 77.95 36.54 34.59 13.02 9.03 6.83 2.64 11.91 8.26 2.99 3.84 2.65 | 78.09 36.70 34.92 12.96 8.95 6.47 2.98 10.54 8.03 3.26 3.58 2.51 | 73.16 34.34 33.72 14.75 12.09 5.10 1.19 9.58 7.79 3.10 3.42 2.32 |
| C 2 -～C 5 -, heavy % iC 4 -+iC 5 -, heavy % | 24.51 6.11 | 26.65 5.64 | 25.13 5.77 | 21.98 5.42 |
Example 7
Provided by the invention is that active ingredient, clay are that matrix, aluminium colloidal sol are the Preparation of catalysts and the cracking performance thereof of binding agent with P-ZRP and USY.
At 193 kilograms aluminium colloidal sols (Zhou village, Shandong catalyst plant product, Al
2O
311.4%, pH2～3) 72.6 kilograms of halloysites of middle adding, stirred 90 minutes, add again and contain 25 kilograms of P-ZRP and USY (Zhou village, Shandong catalyst plant product, SiO
2/ Al
2O
3≮ 10) the decationized Y sieve aqueous slurry of zeolite mixture stirs, and spray drying forming promptly gets catalyst sample G.
Listed the composition of this catalyzer in the table 10.For the purpose of contrast, (note is done contrast 4 to have listed file names with catalyzer described in the example 1 of CN1072201A in the table 10, its active ingredient is ZSM-5, DASY and REY zeolite mixture) and the example 1 of CN1085825A described in catalyzer (note is done contrast 5, and its active ingredient is ZRP, DASY and REY zeolite mixture).
Be that raw material is estimated above-mentioned catalyst sample with the paraffinic base wax oil on the small fixed flowing bed device, appreciation condition is with example 1, and evaluation result sees Table 11.
Table 10
| Catalyzer | G | Contrast 4 | Contrast 5 |
| Catalyst forms, and heavy % kaolin alumina zeolites is P-ZRP USY DASY REY ZSM-5 ZRP wherein | 53.0 22.0 25.0 60.0 40.0 0.0 0.0 0.0 0.0 | 53.2 16.8 30.0 0.0 0.0 33.4 50.0 16.6 0.0 | 53.2 16.8 30.0 0.0 0.0 33.4 50.0 0.0 16.6 |
Table 11
| Catalyzer | G | Contrast 4 | Contrast 5 |
| Transformation efficiency, heavy % product distributes, heavy % reacted gas gasoline (C 5～221 ℃) diesel oil (221～330 ℃) heavy oil (＞330 ℃) coke olefins yield wherein, heavy % C 2 - C 3 -Total C 4 -Different C 4 -Total C 5 -Different C 5 - | 83.38 43.52 35.85 8.31 8.31 4.01 2.54 14.84 12.49 4.29 5.00 3.51 | 85.50 33.10 47.00 9.20 5.30 5.40 0.91 9.75 7.45 2.53 3.40 2.31 | 86.18 34.63 46.24 9.16 4.62 5.35 0.96 10.30 7.87 2.67 3.59 2.44 |
| C 2 -～C 5 -, heavy % iC 4 -+iC 5 -, heavy % | 34.87 7.80 | 21.51 4.84 | 22.72 5.11 |
Example 8
Provided by the invention is that active ingredient, clay are that matrix, pseudo-boehmite and silicon sol are the Preparation of catalysts and the cracking performance thereof of binding agent with P-ZRP with the high silicon Y that contains rare earth.
With 175 kilograms of decationized Y sieve water 61.6 kilograms of halloysites are pulled an oar, add 75 kilograms pseudo-boehmite and 24.5 kilograms silicon sol (Zhou village, Shandong catalyst plant product, SiO
224.49%), stirred 90 minutes, add again and contain 25 kilograms of P-ZRP and REUSY (Zhou village, Shandong catalyst plant product, RE
2O
3≤ 3%) the decationized Y sieve aqueous slurry of zeolite mixture stirs, and spray drying forming promptly gets catalyst sample H.
Listed the composition of this catalyzer in the table 12.Be that raw material is estimated it with the paraffinic base wax oil on the small fixed flowing bed device, appreciation condition is with example 1, and evaluation result sees Table 13.
Example 9
Provided by the invention is that active ingredient, amorphous aluminum silicide are the Preparation of catalysts and the cracking performance thereof of matrix with P-ZRP and USY.
With 373 premium on currency glass (Zhou village, Shandong catalyst plant product, modulus 3.2 ± 0.1, SiO
2124 ± 2.0 grams per liters) with the dilution of 398 kilograms decationized Y sieve water, Tai-Ace S 150 (Zhou village, the Shandong catalyst plant product) solution that to add 97 liters of alumina contents be 50 grams per liters, stir, its temperature is controlled at 15～25 ℃, alum liquor and 95 liters of ammoniacal liquor that to add 136 liters of alumina contents successively again be 90 grams per liters, stirring promptly gets carrier pulp.Zeolite mixture is mixed spray drying forming behind the homogeneous, the flush away Na that dissociates with above-mentioned carrier pulp with the slurries of decationized Y sieve water
+, be drying to obtain catalyst sample I.
Listed the composition of this catalyzer in the table 12.Be that raw material is estimated it with the paraffinic base wax oil on the small fixed flowing bed device, appreciation condition is with example 1, and evaluation result sees Table 13.
Table 12
| Catalyzer | H | I |
| Catalyst forms, and heavy % kaolin aluminium oxide silica amorphous aluminum silicide zeolite is P-ZRP REUSY USY wherein | 45.0 24.0 6.0 0.0 25.0 60.0 40.0 0.0 | 0.0 0.0 0.0 75.0 25.0 50.0 0.0 50.0 |
Table 13
| Catalyzer | H | I |
| Transformation efficiency, heavy % product distributes, heavy % reacted gas gasoline (C 5～221 ℃) diesel oil (221～330 ℃) heavy oil (＞330 ℃) coke olefins yield wherein, heavy % C 2 - C 3 -Total C 4 -Different C 4 -Total C 5 -Different C 5 - | 87.57 45.44 38.22 8.74 3.69 3.91 2.84 16.27 13.10 5.16 5.75 4.02 | 88.37 48.53 34.93 7.81 3.82 4.91 2.93 17.51 13.40 5.73 5.35 3.74 |
| C 2 -～C 5 -, heavy % iC 4 -+iC 5 -, heavy % | 37.96 9.18 | 39.19 9.47 |
Claims (10)
1. catalyzer that is used to produce low-carbon alkene, forms by the inorganic oxide of the clay of 0～70 heavy %, 5～90 heavy % and the zeolites of 10～40 heavy %, it is characterized in that said zeolite is the type-Y high silicon zeolite of the five-ring supersiliceous zeolite of phosphorous and rare earth of 25～75 heavy % and 25～75 weight % or the mixture that contains the y-type zeolite of rare earth.
2. according to the described catalyzer of claim 1, it is characterized in that said clay is selected from kaolin and/or halloysite.
3. according to the described catalyzer of claim 1, it is characterized in that said inorganic oxide is selected from SiO
2Al
2O
3, Al
2O
3Or/and SiO
2
4. according to the described catalyzer of claim 1, it is characterized in that said high-silicon Y-Zeolite with chemistry and/or physical method handle, contain or do not contain the y-type zeolite of the stabilization of rare earth.
5. according to the described catalyzer of claim 1, it is characterized in that the said rare earth Y type zeolite that contains is selected from Rare Earth Y, rare earth hydrogen Y.
6. according to the described catalyzer of claim 1, it is characterized in that said phosphorous and five-ring supersiliceous zeolite rare earth is to handle obtain phosphorous (with P with aluminum phosphate
2O
5Meter) 2～20 heavy %'s contains the rare-earth five-membered ring supersiliceous zeolite.
7. according to the described catalyzer of claim 1, it is characterized in that said phosphorous and five-ring supersiliceous zeolite rare earth is to handle obtain phosphorous (with P with aluminum phosphate
2O
5Meter) 2～10 heavy %'s contains the rare-earth five-membered ring supersiliceous zeolite.
8. according to claim 6 or 7 described catalyzer, it is characterized in that the said X-ray diffractogram that the rare-earth five-membered ring supersiliceous zeolite has ZSM-5 zeolite family that contains, its anhydrous chemical constitution formula is 0.01～0.30RE
2O
30.4～1.0Na
2OAl
2O
320～60SiO
2, the used crystal seed when synthetic of the rare earth in the composition, this zeolite are 2～4 times of ZSM-5 zeolite to the ratio of normal hexane and hexanaphthene adsorptive capacity.
9. according to claim 6 or 7 described catalyzer, it is characterized in that the said rare-earth five-membered ring supersiliceous zeolite that contains is that employing water glass, aluminum phosphate and mineral acid are raw material, with Rare Earth Y or rare earth hydrogen Y zeolite is crystal seed, makes in 12～60 hours at 130～200 ℃ of following crystallizations.
10. according to claim 6 or 7 described catalyzer, it is characterized in that saidly handling the method that contains the rare-earth five-membered ring supersiliceous zeolite with aluminum phosphate and being: zeolite is exchanged processing in advance with ammonium ion, make its sodium content (with Na
2O meter) reduces to and be not more than 0.1 heavy %, will consist of Al
2O
3: P
2O
5=1: 1～3 aluminum phosphate colloid is according to P
2O
5: weight ratio and this zeolite of zeolite (butt)=1: 5～99 mix, and roasting is 0.5～6 hour in the presence of 300～600 ℃, 10～100% water vapors.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94114963A CN1053918C (en) | 1994-08-22 | 1994-08-22 | Double zeolite catalyst for prepn. of low carbon olefine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94114963A CN1053918C (en) | 1994-08-22 | 1994-08-22 | Double zeolite catalyst for prepn. of low carbon olefine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1117518A CN1117518A (en) | 1996-02-28 |
| CN1053918C true CN1053918C (en) | 2000-06-28 |
Family
ID=5037300
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94114963A Expired - Lifetime CN1053918C (en) | 1994-08-22 | 1994-08-22 | Double zeolite catalyst for prepn. of low carbon olefine |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1053918C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1102634C (en) * | 1997-10-15 | 2003-03-05 | 中国石油化工集团公司 | Catalyst for catalytic thermal cracking process to prepare lower olefine |
| 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 |
| CN102247884B (en) * | 2011-05-20 | 2012-10-24 | 天津大沽化工股份有限公司 | Catalyst used in process of preparing vinyl chloride from 1,2-ethylene dichloride and preparation method of catalyst |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0188841A1 (en) * | 1984-12-21 | 1986-07-30 | Catalysts & Chemicals Industries Co., Ltd. | Hydrocarbon catalytic cracking catalyst compositions and method therefor |
| CN1062157A (en) * | 1991-10-24 | 1992-06-24 | 中国石油化工总公司石油化工科学研究院 | The cracking catalyst and the preparation of phosphorous and hydrogen Y molecular sieve |
| CN1082093A (en) * | 1992-08-14 | 1994-02-16 | 中国石油化工总公司 | Improve the auxiliary agent of gasoline octane rating and increase by third, butylene productive rate |
| CN1085825A (en) * | 1992-10-22 | 1994-04-27 | 中国石油化工总公司 | Produce the hydrocarbon conversion catalyst of premium-type gasoline, propylene, butylene |
-
1994
- 1994-08-22 CN CN94114963A patent/CN1053918C/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0188841A1 (en) * | 1984-12-21 | 1986-07-30 | Catalysts & Chemicals Industries Co., Ltd. | Hydrocarbon catalytic cracking catalyst compositions and method therefor |
| CN1062157A (en) * | 1991-10-24 | 1992-06-24 | 中国石油化工总公司石油化工科学研究院 | The cracking catalyst and the preparation of phosphorous and hydrogen Y molecular sieve |
| CN1082093A (en) * | 1992-08-14 | 1994-02-16 | 中国石油化工总公司 | Improve the auxiliary agent of gasoline octane rating and increase by third, butylene productive rate |
| CN1085825A (en) * | 1992-10-22 | 1994-04-27 | 中国石油化工总公司 | Produce the hydrocarbon conversion catalyst of premium-type gasoline, propylene, butylene |
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| Publication number | Publication date |
|---|---|
| CN1117518A (en) | 1996-02-28 |
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