CN100537714C - A kind of deep pyrolytic catalyst of heavy oil - Google Patents
A kind of deep pyrolytic catalyst of heavy oil Download PDFInfo
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- CN100537714C CN100537714C CNB2005101054404A CN200510105440A CN100537714C CN 100537714 C CN100537714 C CN 100537714C CN B2005101054404 A CNB2005101054404 A CN B2005101054404A CN 200510105440 A CN200510105440 A CN 200510105440A CN 100537714 C CN100537714 C CN 100537714C
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Abstract
A kind of deep pyrolytic catalyst of heavy oil, form by active ingredient and matrix, it is characterized in that said active ingredient contains the ultra-steady Y molecular sieve of the penta-basic cyclic molecular sieve of 5.0-60.0 weight %, 5.0-40.0 weight % and the SAPO-11 molecular sieve of 1.0-50.0 weight %, said SAPO-11 molecular sieve, X ray diffracting data before its roasting removed template method is as shown in table 1, X ray diffracting data behind the roasting removed template method is as shown in table 2, and mole is Al when forming with the anhydrous chemical formulation of oxide form
2O
3: (0.60-1.20) P
2O
5: (0.05-1.30) SiO
2This catalyzer has higher olefine selective and productivity of propylene, is fit to the degree of depth catalytic pyrolysis of mink cell focus.
Description
Technical field
The invention relates to a kind of catalyst for cracking, more specifically say so about the catalyzer of heavy oil deep cracking producing light olefins.
Background technology
Along with the continuous enhancing of social material requisite, the consumption of ethene and propylene is in cumulative year after year, and these the two kinds of products particularly latter's market outlook are very good.Yet most of propylene is from ethylene industry, and cost is very high, and yield potential is little, is difficult to satisfy the requirement of market to output.
The beginning of the nineties, Research Institute of Petro-Chemical Engineering successfully industrialization mink cell focus preparing low-carbon olefin by catalytically cracking Technology, its productivity of propylene can bring up to 16
-20m%.Because the raw materials cost that adopts is lower, and service temperature, is popular at petrochemical industry so the cost of this technological process production propylene is also very low far below the naphtha steam cracking temperature.
For the method for catalytic cracking producing light olefins, be that the patent of representative uses metal to be active ingredient with USP3541179, USP3647682, DD225135, SU1214726 etc., be the preparing carriers catalyzer with silicon oxide, aluminum oxide etc.This catalyzer dehydrogenation reaction when catalytic cracking generates low-carbon alkene is also carried out in a large number, and coking problem is serious on the catalyzer.
Temperature of reaction height when using solid acid catalyst, require the reaction raw materials lightweight, and equipment corrosion is serious, ethylene content is more in the product, is unfavorable for propylene enhancing.
Patents such as USP4309280, USP4521298, USP4552648, USP3758403 have also increased the yield of low-carbon alkene when improving gasoline octane rating.Its activity of such catalysts component is large pore molecular sieve (Y or X type) and shape-selective molecular sieve ZSM-5.
CN1083092A uses the catalyzer that contains glue connection rectorite leng layered molecular sieve and/or contain the rare-earth five-membered ring high-silica zeolite, 680
-780 ℃ of temperature range cracking heavy hydrocarbon classes can obtain the ethene of 23m%, and total productivity of low carbon olefin hydrocarbon is 50m%.
Summary of the invention
Heavy-oil catalytic thermal cracking (DCC) general operation is 515
-660 ℃ of temperature ranges are than the service temperature height of general FCC technology riser tube.Therefore, the cracking reaction of DCC is fast, has certain secondary cracking reaction, and the ratio of control primary first-order equation and secondary reaction becomes one of key of Catalyst Design.
The SAPO-11 molecular sieve is the phosphorus aluminium si molecular sieves with AEL structure, and its unit cell parameters is: a=8.312
, b=18.729
, c=13.392
, its structure cell is little, and it is good that selectivity of light olefin sieves than ZSM-5 types of molecules.
A kind of SAPO-11 molecular sieve with superior structural stability is disclosed in CN1283587A, this molecular sieve is the template preparation with di-n-propylamine and/or Diisopropylamine, XRD spectra data before and after its removed template method are basic identical, the crystalline structure that still keeps the Ima2 spacer, has good structural stability, this molecular sieve is when supported palladium or platinum are used for hydroisomerization reaction of alkane later on, and its isomerization selectivity and isomerization product yield obviously improve.And the present inventor is surprised to find that, when including the disclosed SAPO-11 molecular sieve among the CN1283587A in the catalytic cracking catalyst component, with adopting conventional SAPO-11 molecular sieve is that the catalyzer of component is compared, and catalyzer propylene selectivity increases, and productive rate can improve 1
-3 percentage points.
Therefore, the object of the present invention is to provide a kind of have higher olefine selective and productivity of propylene, be fit to the degree of depth catalytic pyrolysis of mink cell focus, can be at the deep pyrolytic catalyst of heavy oil of the productive rate of propylene particularly of increased low carbon olefine output under the lower cost.
Deep pyrolytic catalyst of heavy oil provided by the invention, form by active ingredient and matrix, it is characterized in that said active ingredient contains the ultra-steady Y molecular sieve of the penta-basic cyclic molecular sieve of 5.0-60.0 weight %, 5.0-40.0 weight % and the SAPO-11 molecular sieve of 1.0-50.0 weight %, said SAPO-11 molecular sieve, X ray diffracting data before its roasting removed template method is as shown in table 1, X ray diffracting data behind the roasting removed template method is as shown in table 2, and mole is Al when forming with the anhydrous chemical formulation of oxide form
2O
3: (0.60-1.20) P
2O
5: (0.05-1.30) SiO
2, before the roasting removed template method with the roasting removed template method after the crystalline structure of molecular sieve have the spacer of identical Ima2, in the table, m, s and vs represent relative intensity, m:20-70, s:70-90, vs:90-100.
Table 1
Table 2
In the catalyzer provided by the invention, the SiO of said penta-basic cyclic molecular sieve
2/ Al
2O
3Than between 20-500, can be ZSM-5, or the ZSM-5 of phosphorus modification, or with phosphorus be selected from the ZSM-5 of transition-metal Fe, Co or Ni modification.
In the catalyzer provided by the invention, the lattice constant of said ultra-steady Y molecular sieve is at 24.20-24.40
Between, can be the HSY of Hydrogen, also can be the ReSY of rare earth exchanged, the content of rare earth is with RE
2O
3Count 0-10.0%.
In the catalyzer provided by the invention, said SAPO-11 molecular sieve is according to disclosed method preparation among the CN1283587A, specifically, this molecular sieve is to obtain by following method is synthetic: aluminium source, silicon source, phosphorus source and organic formwork agent are mixed into glue, make mole and consist of aR:Al
2O
3: bP
2O
5: cSiO
2: dH
2The reaction mixture of O, then with this mixture hydrothermal crystallizing, and with crystallization product filtration, washing, drying, temperature during wherein said one-tenth glue is 25～60 ℃, the condition of said crystallization is a hydrothermal crystallizing 4～60 hours under 140～190 ℃ temperature and autogenous pressure, and wherein the value of a is 0.2～2.0, and the value of b is 0.6～1.2, the value of c is 0.1～1.5, and the value of d is 15～50.
In the catalyzer provided by the invention, said matrix is selected from one or more the mixture in the following material: kaolin, pseudo-boehmite or aluminum oxide, silicon sol or aluminium colloidal sol.With the catalyzer is benchmark, and kaolinic content is 10.0
-80.0 the content of weight %, pseudo-boehmite or aluminum oxide is 12.0
-60.0 the content of weight %, silicon sol or aluminium colloidal sol is 1.0
-50.0 weight %.
The invention provides catalyzer can prepare through following method:
1) the clay making beating 10
-120 minutes, add pseudo-boehmite or aluminum oxide powder or its slurries and stir 5
-100 minutes, add acid (hydrochloric acid, nitric acid, sulfuric acid, formic acid, acetate etc.) again and make slurries be acid, PH is 1.5
-4.5 scope is warming up to 40-100 ℃ of temperature range, stops to stir aging 10
-120 minutes.
2) SAPO-11, penta-basic cyclic molecular sieve and Y molecular sieve are mixed by a certain percentage, pull an oar homogeneous 5
-100 minutes, mix with step 1) gained slurry then, homogeneous, carry out moulding then.Forming method comprises: spraying drying, extrusion etc., with the material after the moulding wash, filter, drying or roasting promptly get catalyst prod.
This catalyzer has higher olefine selective and productivity of propylene, is fit to the degree of depth catalytic pyrolysis of mink cell focus, can be at the productive rate of propylene particularly of increased low carbon olefine output under the lower cost.
Embodiment
The invention will be further described below by embodiment, but content not thereby limiting the invention.
Prepare the SAPO-11 molecular sieve with 1,2,3,7, the 8 disclosed methods of embodiment among the CN1283587A, the forward and backward XRD spectra of their roastings meets the data of table 1, table 2, and the mole composition is respectively:
Sample Z1:Al
2O
3: 0.85 P
2O
5: 0.55 SiO
2
Sample Z2:Al
2O
3: 0.92 P
2O
5: 0.40 SiO
2
Sample Z3:Al
2O
3: 0.90 P
2O
5: 1.02 SiO
2
Sample Z4:Al
2O
3: 0.90 P
2O
5: 0.43 SiO
2
Sample Z5:Al
2O
3: 0.91 P
2O
5: 0.73 SiO
2
Comparative sample D: with the sample of the disclosed methods preparation of Comparative Examples among the CN1283587A 2 SAPO-11 molecular sieve as a comparison, mole consists of: Al
2O
3: 0.83 P
2O
5: 0.50 SiO
2
Embodiment 1
100 gram Suzhou carclazytes (butt) and 300 ml deionized water are mixed the back add 10 milliliters of concentrated hydrochloric acids, stirred 10 minutes, add 50 gram pseudo-boehmites (butt) and stirred 50 minutes.60
-Aging these slurries of 70 ℃ of temperature ranges 60 minutes.(lattice constant is less than 24.4 for hyperastable Y-type RE molecular sieve, Shandong Zibo production with DASY with Z1, ZRP (silica alumina ratio 30, degree of crystallinity is greater than 80% for penta-basic cyclic molecular sieve, Shandong Zibo production)
, content of rare earth is less than 3%) mix, mix with slurries after aging, after spray-dried, washing, the drying catalyzer Cat-1:Z1 content be that 16.0m%, ZRP content are that 4.0m%, DASY content are 4.0m%, all the other are matrix.
Comparative Examples
100 gram Suzhou carclazytes (butt) and 300 ml deionized water are mixed the back add 10 milliliters of concentrated hydrochloric acids, stirred 10 minutes, add 50 gram pseudo-boehmites (butt) and stirred 50 minutes.60
-Aging these slurries of 70 ℃ of temperature ranges 60 minutes.SAPO-11 molecular sieve comparative sample D, ZRP and DASY are mixed, mix with the slurries after aging, getting comparative catalyst DB-Cat:D content after spraying drying and washing, the drying is that 16.0m%, ZRP content are that 4.0m%, DASY content are 4.0m%, and all the other are matrix.
Embodiment 2
With embodiment 1, difference is that ZRP replaces with ZSP (silica alumina ratio 30, degree of crystallinity is greater than 80%, iron level is less than 2.0% for penta-basic cyclic molecular sieve, Shandong Zibo production).
Cat-2:Z1 content is that 16.0m%, ZSP content are that 4.0m%, DASY content are 4.0m%, and all the other are matrix.
Embodiment 3
With embodiment 1 method, difference is that ZRP replaces with ZSM-5 (silica alumina ratio is 30 for penta-basic cyclic molecular sieve, the production of Shi Ke institute).
Cat-3:Z1 content is that 16.0m%, ZSM-5 content are that 4.0m%, DASY content are 4.0m%, and all the other are matrix.
Embodiment 4
With embodiment 1 method, difference is the content of each active ingredient.
Cat-4:Z1 content is that 6.0m%, ZRP content are that 4.0m%, DASY content are 4.0m%, and all the other are matrix.
Embodiment 5
With embodiment 1 method, difference is the content of each active ingredient.
Cat-5:Z1 content is that 10.0m%, ZRP content are that 4.0m%, DASY content are 4.0m%, and all the other are matrix.
Embodiment 6
With embodiment 2 methods, difference is the content of each active ingredient.
Cat-6:Z1 content is that 10.0m%, ZSP content are that 4.0m%, DASY content are 4.0m%, and all the other are matrix.
Embodiment 7-10
With embodiment 1 method, difference is that Z1 replaces with Z2, Z3, Z4, Z5 respectively.
Cat-7:Z2 content is that 16.0m%, ZRP content are that 4.0m%, DASY content are 4.0m%, and all the other are matrix.
Cat-8:Z3 content is that 16.0m%, ZRP content are that 4.0m%, DASY content are 4.0m%, and all the other are matrix.
Cat-9:Z4 content is that 16.0m%, ZRP content are that 4.0m%, DASY content are 4.0m%, and all the other are matrix.
Cat-10:Z5 content is that 16.0m%, ZRP content are that 4.0m%, DASY content are 4.0m%, and all the other are matrix.
Embodiment 11
On small fixed flowing bed (FFB) device, under 560 ℃ of temperature of reaction, utilize 30% grand celebration VR (character sees Table 3) that above catalyzer is estimated.
Appreciation condition: weight hourly space velocity is 4.0h
-1, agent-oil ratio is 10, steam/charging is 0.25.
Cat-1
-The evaluation result of Cat-6 and comparative catalyst DB-Cat sees Table 4.
Cat-7
-The evaluation result of Cat-10 sees Table 5.
Table 3
| Stock oil | 30％VR |
| Density, g/cm 3Kinematic viscosity, mm 280 ℃ of 100 ℃ of condensation points of/s, ℃ aniline point, ℃ carbon residue, m% refractive index n D 70 | 0.8905 39.83 22.13 49 97.8 2.94 1.4798 |
| Elementary composition, m% C H S N | 86.55 13.18 0.15 0.19 |
| Group composition, m% stable hydrocarbon aromatic hydrocarbons gum asphalt | 64.5 24.2 11.1 0.2 |
| Metal content, ppm Fe Ni Cu V boiling range, ℃ initial boiling point 5% 10% 30% 50% 70% | 3.2 2.9 <0.1 <0.1 261 402 439 501 550 565(56.0％) |
Table 4
| Catalyzer | DB-Cat | Cat-1 | Cat-2 | Cat-3 | Cat-4 | Cat-5 | Cat-6 |
| Material balance, m% dry gas liquefied gas C5 gasoline, diesel heavy oil coke amounts to | 7.96 39.67 28.05 11.54 7.76 5.01 99.99 | 6.19 42.03 27.88 10.43 8.33 5.13 99.99 | 3.63 42.75 29.03 10.64 9.29 4.65 99.99 | 10.46 40.82 25.97 10.09 6.72 5.92 99.98 | 7.90 41.54 27.12 10.30 7.68 5.44 99.98 | 7.05 41.79 27.50 10.37 8.01 5.29 100.1 | 8.35 41.15 27.65 10.5 8.5 5.31 101.46 |
| Transformation efficiency, m% | 80.68 | 80.61 | 79.06 | 83.18 | 81.64 | 81.23 | 80.69 |
| Gas composition, m% hydrogen methane ethane and ethylene propane propylene Trimethylmethane normal butane butene-1 iso-butylene is anti--and butene-2 is suitable-butene-2 divinyl-1,3 | 0.94 4.11 2.06 9.58 8.18 36.76 14.73 2.88 3.79 8.23 4.94 3.72 0.08 | 0.60 3.14 1.91 8.25 8.17 37.60 14.79 2.64 3.61 9.46 5.61 4.15 0.07 | 0.51 2.48 1.47 5.53 6.27 39.86 15.34 2.08 3.94 11.01 6.59 4.84 0.07 | 0.74 4.25 2.63 12.77 10.34 34.83 13.87 3.57 3.06 6.88 3.98 3.01 0.07 | 0.65 3.59 2.20 10.06 9.44 36.09 14.42 3.01 3.39 8.43 4.96 3.70 0.07 | 0.63 3.37 2.05 9.15 8.81 36.85 14.61 2.83 3.50 8.95 5.29 3.93 0.07 | 0.57 2.48 1.49 8.53 7.27 36.89 13.23 2.09 3.93 12.01 6.60 4.83 0.07 |
| Gas yield, m% hydrogen yield ethylene yield productivity of propylene iso-butylene | 0.45 4.57 17.52 3.92 | 0.29 4.06 18.13 4.11 | 0.24 2.56 18.48 4.45 | 0.38 6.55 17.86 3.53 | 0.33 5.05 17.84 3.88 | 0.31 4.56 17.99 3.99 | 0.28 4.22 18.26 4.95 |
| Gasoline family forms, m% normal paraffin isoparaffin alkene naphthenic hydrocarbon aromatic hydrocarbons | 2.98 6.72 11.58 4.30 73.63 | 4.75 12.15 22.56 6.18 53.57 | 5.80 15.76 30.29 7.35 40.00 | 3.00 6.12 9.68 4.23 76.18 | 4.05 9.74 17.41 5.40 62.61 | 4.40 10.94 19.99 5.79 58.09 | 5.60 15.56 30.09 7.15 41.60 |
| Octane value MON RON | 80.60 96.87 | 80.69 94.61 | 80.13 92.87 | 81.63 97.50 | 81.07 95.76 | 80.88 95.19 | 80.10 93.37 |
Table 5
| Catalyzer | Cat-7 | Cat-8 | Cat-9 | Cat-10 |
| Material balance, m% dry gas liquefied gas C5 gasoline, diesel heavy oil coke amounts to | 7.01 42.23 27.56 10.21 7.16 5.83 100 | 5.87 40.31 28.76 11.81 8.28 4.97 100 | 6.76 41.66 27.97 10.57 7.06 5.98 100 | 6.13 40.01 28.6 11.93 8.12 5.21 100 |
| Transformation efficiency, m% | 81.21 | 79.53 | 81.56 | 80.36 |
| Gas yield, m% hydrogen yield ethylene yield productivity of propylene iso-butylene | 0.31 4.27 17.83 4.52 | 0.26 3.82 17.77 3.79 | 0.30 4.25 17.59 4.38 | 0.32 4.12 18.19 4.24 |
| Gasoline family forms, m% normal paraffin isoparaffin alkene naphthenic hydrocarbon aromatic hydrocarbons | 4.81 12.73 21.35 6.39 54.23 | 5.42 13.82 30.81 6.23 43.72 | 4.76 12.65 25.03 6.27 51.29 | 5.11 13.34 29.58 6.12 45.85 |
Claims (7)
1. deep pyrolytic catalyst of heavy oil, form by active ingredient and matrix, it is characterized in that said active ingredient contains the ultra-steady Y molecular sieve of the penta-basic cyclic molecular sieve of 5.0-60.0 weight %, 5.0-40.0 weight % and the SAPO-11 molecular sieve of 1.0-50.0 weight %, said SAPO-11 molecular sieve, X ray diffracting data before its roasting removed template method is as shown in table 1, X ray diffracting data behind the roasting removed template method is as shown in table 2, and mole is Al when forming with the anhydrous chemical formulation of oxide form
2O
3: (0.60-1.20) P
2O
5: (0.05-1.30) SiO
2, before the roasting removed template method with the roasting removed template method after the crystalline structure of molecular sieve have the spacer of identical Ima2, in the table, m, s and vs represent relative intensity, m:20-70, s:70-90, vs:90-100,
Table 1
Table 2
2. according to the catalyzer of claim 1, said penta-basic cyclic molecular sieve is ZSM-5.
3. according to the catalyzer of claim 1, said penta-basic cyclic molecular sieve is the ZSM-5 of phosphorus modification.
4. according to the catalyzer of claim 3, said penta-basic cyclic molecular sieve obtains with transition-metal Fe, Co or Ni modification.
5. according to the catalyzer of claim 1, the lattice constant of said ultra-steady Y molecular sieve is at 24.20-24.40
Between, the content of the rare earth of molecular sieve is with RE
2O
3Count 0-10.0%.
6. according to the catalyzer of claim 1, said SAPO-11 molecular sieve is to obtain by following method is synthetic: aluminium source, silicon source, phosphorus source and organic formwork agent are mixed into glue, make mole and consist of aR:Al
2O
3: bP
2O
5: cSiO
2: dH
2The reaction mixture of O, then with this mixture hydrothermal crystallizing, and with crystallization product filtration, washing, drying, temperature during wherein said one-tenth glue is 25～60 ℃, the condition of said crystallization is a hydrothermal crystallizing 4～60 hours under 140～190 ℃ temperature and autogenous pressure, and wherein the value of a is 0.2～2.0, and the value of b is 0.6～1.2, the value of c is 0.1～1.5, and the value of d is 15～50.
7. according to the catalyzer of claim 1, wherein said active ingredient is made up of the penta-basic cyclic molecular sieve of 5.0-60.0 weight %, the ultra-steady Y molecular sieve of 5.0-40.0 weight % and the SAPO-11 molecular sieve of 1.0-50.0 weight %.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11066605B2 (en) | 2019-11-12 | 2021-07-20 | Saudi Arabian Oil Company | Systems and methods for catalytic upgrading of vacuum residue to distillate fractions and olefins |
| US11066606B2 (en) | 2019-11-12 | 2021-07-20 | Saudi Arabian Oil Company | Systems and methods for catalytic upgrading of vacuum residue to distillate fractions and olefins with steam |
| US11225612B2 (en) | 2020-03-27 | 2022-01-18 | Saudi Arabian Oil Company | Catalyst and process for catalytic steam cracking of heavy distillate |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101451074B (en) * | 2007-11-28 | 2012-03-21 | 中国石油化工股份有限公司 | Catalyst for heavy oil catalytic cracking and preparation method thereof |
| CN101676028B (en) * | 2008-09-19 | 2012-06-27 | 中国石油化工股份有限公司 | Catalyst for preparing light olefin by carbinol |
| CN101676247B (en) * | 2008-09-19 | 2012-05-30 | 中国石油化工股份有限公司 | Method for preparing low carbon olefin |
| CN101676027B (en) * | 2008-09-19 | 2012-10-10 | 中国石油化工股份有限公司 | Petroleum hydrocarbon cracking catalyst |
-
2005
- 2005-09-28 CN CNB2005101054404A patent/CN100537714C/en active Active
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11066605B2 (en) | 2019-11-12 | 2021-07-20 | Saudi Arabian Oil Company | Systems and methods for catalytic upgrading of vacuum residue to distillate fractions and olefins |
| US11066606B2 (en) | 2019-11-12 | 2021-07-20 | Saudi Arabian Oil Company | Systems and methods for catalytic upgrading of vacuum residue to distillate fractions and olefins with steam |
| US11225612B2 (en) | 2020-03-27 | 2022-01-18 | Saudi Arabian Oil Company | Catalyst and process for catalytic steam cracking of heavy distillate |
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