CN1785518A - Catalytic cracking catalyst of propylene and ethylene and its preparation method - Google Patents
Catalytic cracking catalyst of propylene and ethylene and its preparation method Download PDFInfo
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- CN1785518A CN1785518A CNA2004101009565A CN200410100956A CN1785518A CN 1785518 A CN1785518 A CN 1785518A CN A2004101009565 A CNA2004101009565 A CN A2004101009565A CN 200410100956 A CN200410100956 A CN 200410100956A CN 1785518 A CN1785518 A CN 1785518A
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- zeolite
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- propylene
- ethene
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
A catalyst for preparing propene and ethene by catalytic cracking is composed of kaolinite (3-50%), Al2O3 (5-95%) and high-Si zeolite (2-50%). Its advantages are high hydrothermal activity and stability, high conversion rate and high output rate of propene and ethene.
Description
Technical field
The present invention relates to catalytic cracking catalyst of a kind of propylene and ethene and preparation method thereof.
Background technology
Propylene and ethene are important petrochemical industry base stocks, and the preparation method that adopts is to be the pyrolysis in tubular furnace of raw material with the naphtha usually; With the natural gas is the steam cracking of raw material; The heat carrier cracking of heavy hydrocarbon and with the method for low-carbon alcohols catalyzed conversion.Catalytic cracking unit commonly used is also paid when producing gasoline and light diesel fuel and is produced ethene and propylene, and its output accounts for below 15% (mass percent) of feedstock oil.
Ethene, propylene occupy important status as basic Organic Chemicals in economy, its demand is also in constantly increasing.And in its production process, generating has a large amount of carbon four, C5 fraction byproduct.For a long time, only some is converted into other products to these byproducts, and all the other major parts are used as fuel consumption and have fallen.This has not only increased the cost of investment of ethene, also causes the significant wastage of resource.Ethene, the propylene of the carbon four of these low values, high added value that C5 fraction is converted into urgent need not only considerable economic will be if can produced, and also the huge social benefit can be brought.
From document, be that raw material adopts cracking or cleavage method to produce propylene and ethene with the C 4 olefin, mainly by two kinds of technology.A kind of is the purpose that reaches conversion by disproportionated reaction.But in this conversion process, need just can obtain propylene as raw material and with ethylene reaction with highly purified 2-butylene or 2-amylene.(U.S.P50,43,522 and U.S.P50,26,936), and the catalyst that adopts is the ZSM-5 molecular sieve, except that ethene, propylene, much is difficult to the accessory substance that separates in addition in the product.The separation of product is very difficult.
Another kind of conversion process adopts catalytic cracking technology to achieve the goal.Its maximum characteristics are: 1, the free degree of raw material is big.2, do not need to remove the preprocessing process of 1-butylene, isobutene.3, can obtain ethene and propylene simultaneously.Lurgi company has developed and a kind of carbon four, carbon pentaene hydrocarbon has been converted into the fixed bed catalytic cracking technology of ethene and propylene, 60% carbon four, the C5 fraction that generates in the steam cracking process can be converted into propylene, makes the propylene/ethylene productivity ratio bring up to 1.0.This technical process adopts the ZSM-5 molecular sieve as catalyst.
In addition, Arco company has developed a kind of technology that can make the low value lighter hydrocarbons be transformed into the propylene of high value.This technology that is called as Superflex by to carrying out deep processing through the thermal cracking C-4-fraction after the selection hydrotreatment, can obtain being higher than 40% productivity of propylene.This technology is higher to the selectivity of light hydrocarbon, can be ethene and propylene with 2/3 feedstock conversion, with the supporting use of ethylene unit, has improved total propylene/ethylene ratio.This technical process also with the ZSM-5 molecular sieve as catalyst.United States Patent (USP) U.S.P6 has reported that a kind of non-zeolite molecular sieve catalyst of the SAPO of employing series is converted into the 2-butylene technology of ethene and propylene in 049,017.These process using fixed bed reactors.The conversion ratio of 2-butylene can reach 66%.In addition, patent WO P01/81280 A1 discloses a kind of with C
4-C
9Alkene is converted into the catalytic cracking technology of ethene and propylene.This process using ZSM-23 molecular sieve is as catalyst.Its yield of ethene is 7.7%, and propene yield is 25%.Butene conversion is up to 76.4%.But this molecular sieve catalyst is at 800 ℃, and after 100% steam was handled down, it is active to descend approximately 23%, and so far, the domestic deep processing and utilization to carbon four, C5 fraction of China still is in the starting stage.
Summary of the invention
The purpose of this invention is to provide catalytic cracking catalyst of a kind of propylene and ethene and preparation method thereof.
Catalytic cracking catalyst of the present invention, it has than HZSM-23 zeolite is the higher hydro-thermal activity stability of catalyst of active component, higher conversion ratio and propene yield.
The catalytic cracking catalyst of a kind of propylene and ethene is characterized in that catalyst is by 3～50% kaolin, 5～95% Al
2O
3And 2～50% zeolite composition, in weight percentage; Zeolite is phosphorous and ten Yuans ring silica-rich zeolites of rare earth, and wherein content of rare earth is with RE
2O
3Count 10-22wt%, RE represents rare earth element, and phosphorus content is with P
2O
5Count the MTT type zeolite of 2～15wt%; Al
2O
3Be selected from boehmite, aluminium colloidal sol or their mixture.
Kaolin in the catalyst of the present invention can be natural or through various chemistry, physical treatment usually as the various kaolin of cracking catalyst carrier.
Zeolite is to prepare according to the method disclosed in the United States Patent (USP) (U.S.P4,076,842).Be raw material promptly, synthesized at 120-200 ℃ of following crystallization 2-10 days with sodium aluminate, inorganic base, pyrrolidines.
Of the present invention ten Yuans ring high silica zeolite catalysts have the x-ray diffraction spectra of ZSM-23 zeolite family, and its anhydrous chemical expression is 0.05-0.3RE
2O
30.4-1Na
2OAl
2O
350-150SiO
2, wherein RE represents rare earth element.
Ten Yuans of the rare earths ring silica-rich zeolite that contains of the present invention obtains after by ion-exchange treatment, the method of handling MTT type zeolite with phosphoric acid is as follows: earlier zeolite is exchanged processing in advance with ammonium chloride solution and make its sodium ions content less than 0.1 weight %, then with 50 weight %H
3PO
4Solution is according to P
2O
5: the weight ratio of zeolite=1: 10-80 and this zeolite mix, stir after 10-40 hour, and at 80-115 ℃ of dry 10-48 hour, in 300-550 ℃, under the nitrogen atmosphere roasting 1-10 hour.
Preparation of catalysts method provided by the invention: at first boehmite, aluminium colloidal sol or their mixture and kaolin are mixed, and make the slurries that solid content is 15-50 weight % with distilled water, after stirring, use inorganic acid, available nitric acid, phosphoric acid or sulfuric acid transfer to about 3-4 with the pH value of slurries, add quantitative zeolite after leaving standstill aging 2-4 hour under 20-80 ℃, homogeneous, after the spray-drying, spend deionised water, dry down at 100-120 ℃ then.
It is that the catalyst of active component has hydro-thermal activity stability height, conversion ratio height and ethene, characteristics that propene yield is high than HZSM-23 molecular sieve that catalyst provided by the invention is used for catalytic pyrolysis.
Cracking catalyst mixed c 4 alkene performance evaluation is carried out on micro-reactor, and catalyst sample is through 800 ℃, 100% steam treatment after 6 hours, at 625 ℃, water-oil factor 0.5, weight space velocity 2.0h
-1When carrying out the cracking performance evaluation under the condition of ml/g, catalyst provided by the invention is high by 20% than the activity of such catalysts reservation degree that with HZSM-23 is active component; The high 10-22% of C 4 olefin conversion ratio; The high 9-19% of ethylene, propylene yield.
The specific embodiment
The present invention is described further for the following examples.
Being prepared as follows of ten Yuans of used phosphorous and rare earth ring silica-rich zeolites among the embodiment: get 50 gram (butt) Na-ZSM-23 molecular sieves, (SiO
2With Al
2O
3Weight ratio=60, RE
2O
3=5wt%), add in the ammonium chloride solution of 500ml 2.3M, 85 ℃ of following ion-exchanges 4 hours, exchange altogether 3 times, spend deionised water after having exchanged at every turn, after exchange was finished, the sodium in the usefulness atomic absorption spectroscopy zeolite was (with Na
2The O meter) content is 0.02wt%.5 gram industrial phosphoric acids (85wt%) are after deionized waters mix with 106.5 grams, add in the zeolite after the above-mentioned ammonium exchange, stir, and after 110 ℃ of following dryings, promptly get phosphorus (with P in aging 4 hours in 800 ℃, 100% water vapour atmosphere
2O
5Meter) content is ten Yuans ring high silicon MTT type zeolites (hereinafter to be referred as P-ERC) of the phosphorous and rare earth of 5wt%.
Adopt the condition of small stationary bed apparatus evaluate catalysts to be among the embodiment: 625 ℃ of reaction temperatures, water-oil factor 0.5, weight space velocity 2h
-1, through 800 ℃, 100% steam treatment 4 hours, loading amount was 10 grams to catalyst sample in advance, reacting raw materials used is mixed c 4 alkene.Its component is as shown in table 1.
Table 1
| Component | Propylene | Butane | Anti-butene-2 | Maleic-2 | Other |
| Content, % | 1.10 | 4.84 | 36.5 | 46.6 | 11.0 |
Embodiment 1
With the P-ERC zeolite is active component, is that matrix, aluminium colloidal sol are the Preparation of catalysts and the cracking performance thereof of binding agent with kaolin.
(Zhou village, Shandong catalyst plant produces, Al at 110 kilograms aluminium colloidal sols
2O
311.4%, PH2-3) the middle 80 kilograms of kaolin (Lanzhou Petrochemical Company product) that add after adding, stirred 2 hours under the room temperature, added 20 kilograms of (butt) P-ERC zeolites and 30 kilograms of deionized waters again, and homogeneous, spray drying forming promptly get catalyst sample A.
By same preparation method, P-ERC zeolite consumption is reduced to 10 kilograms make catalyst sample B.
[comparative example 1] (makes SiO by oneself with the HZSM-23 zeolite
2With Al
2O
3Weight ratio=60, degree of crystallinity is greater than 90%, Na
2O is less than 0.05 heavy %) replace the P-ERC zeolite, make comparative sample 1 according to raw material consumption and the preparation method of sample A.
The composition and the physical and chemical performance of above-mentioned three kinds of samples are listed in table 2.Evaluation result to the sample of above-mentioned preparation on small stationary bed apparatus and micro-reactor is listed in table 3.
As shown in Table 3, when P-ERC in the catalyst was identical with HZSM-23 content, catalyst provided by the invention was that the conversion ratio height of catalyst carbon alkatetraenes of active component is about 4% with HZSM-23, C2
=～C3
=Yield high about 12%.
Table 2
Table 3
Embodiment 2
With the P-ERC zeolite is active component, is that matrix, boehmite are the Preparation of catalysts and the catalytic pyrolysis performance of binding agent with kaolin.
With 185 kilograms of boehmites and 12.5 kilograms of hydrochloric acid, add in 80 ionized waters, add 68 kilograms of aluminium colloidal sols and 110 kilograms of kaolin again, stir, left standstill under the room temperature aging 2 hours, and then add 40 kilograms of (butt) P-ERC zeolites and 60 kilograms of deionized waters, homogeneous, drying, spray-dried again moulding, washing is drying to obtain catalyst sample C.
[to embodiment 2] replaces the P-ERC zeolite to make with the HZSM-23 zeolite with the HZSM-23 zeolite is the comparative sample 2 of active component.
The composition and the physical and chemical performance of above-mentioned two catalyst samples that make are listed in table 4.On small fixed to the table 5 that the results are shown in of the catalytic performance test of catalyst sample.
Table 4
Table 5
| Activity, heavy % gas yield, heavy % is C wherein 2 ＝ C 3 ＝ C 4 ＝ C 2 ＝+C 3 ＝, heavy % | 85.8 56.5 14.3 26.5 16.7 40.8 | 76.2 53.7 12.6 23.2 17.9 35.8 |
As shown in Table 5, catalyst provided by the invention has conversion ratio height, C
2 =+ C
3 =The characteristics that productive rate is high.
Embodiment 3
The present invention is to provide with the P-ERC zeolite is active component, is that matrix, boehmite and aluminium colloidal sol are the Preparation of catalysts and the catalytic pyrolysis performance of binding agent with kaolin.
45 kilograms of boehmites and 7.5 kilograms of hydrochloric acid are added in 60 kilograms of deionized waters, add 30 kilograms of aluminium colloidal sols and 60 kilograms of kaolin again, stir, leave standstill aging 2 hours under the room temperature, and then add 20 kilograms of (butt) P-ERC zeolites and 20 kilograms of deionized waters, homogeneous, dry, spray-dried again moulding, washing is drying to obtain catalyst sample D.
[Comparative Examples 3] replaces the P-ERC zeolite to make with the HZSM-23 zeolite with the HZSM-23 zeolite is the comparative sample 3 of active component.
The composition and the physical and chemical performance of above-mentioned two catalyst samples that make are listed in table 6.On small fixed to the table 7 that the results are shown in of the catalytic performance test of catalyst sample.
Table 6
Table 7
Claims (2)
1, the catalytic cracking catalyst of a kind of propylene and ethene is characterized in that catalyst is by 3～50% kaolin, 5～95% Al
2O
3And 2～50% zeolite composition, in weight percentage; Zeolite is phosphorous and ten Yuans ring silica-rich zeolites of rare earth, and wherein content of rare earth is with RE
2O
3Count 10-22wt%, RE represents rare earth element, and phosphorus content is with P
2O
5Count the MTT type zeolite of 2～15wt%; Al
2O
3Be selected from boehmite, aluminium colloidal sol or their mixture.
2, Preparation of catalysts method as claimed in claim 1, it is characterized in that boehmite, aluminium colloidal sol or their mixture and kaolin are mixed, and make the slurries that solid content is 15-50 weight % with distilled water, after stirring, use inorganic acid, available nitric acid, phosphoric acid or sulfuric acid transfer to about 3-4 with the pH value of slurries, add quantitative zeolite after leaving standstill aging 2-4 hour under 20-80 ℃, homogeneous is after the spray-drying, spend deionised water, dry down at 100-120 ℃ then.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2004101009565A CN1785518A (en) | 2004-12-10 | 2004-12-10 | Catalytic cracking catalyst of propylene and ethylene and its preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2004101009565A CN1785518A (en) | 2004-12-10 | 2004-12-10 | Catalytic cracking catalyst of propylene and ethylene and its preparation method |
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| Publication Number | Publication Date |
|---|---|
| CN1785518A true CN1785518A (en) | 2006-06-14 |
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ID=36783181
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2004101009565A Pending CN1785518A (en) | 2004-12-10 | 2004-12-10 | Catalytic cracking catalyst of propylene and ethylene and its preparation method |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101829592B (en) * | 2009-03-10 | 2012-07-18 | 中国石油天然气股份有限公司 | Preparation method of high-solid content fluid catalytic cracking catalyst |
-
2004
- 2004-12-10 CN CNA2004101009565A patent/CN1785518A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101829592B (en) * | 2009-03-10 | 2012-07-18 | 中国石油天然气股份有限公司 | Preparation method of high-solid content fluid catalytic cracking catalyst |
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