CN1067603C - Metal modified small-porosity P-Si-Al molecular sieve catalyst, its preparing process and use thereof - Google Patents
Metal modified small-porosity P-Si-Al molecular sieve catalyst, its preparing process and use thereof Download PDFInfo
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- CN1067603C CN1067603C CN96115362A CN96115362A CN1067603C CN 1067603 C CN1067603 C CN 1067603C CN 96115362 A CN96115362 A CN 96115362A CN 96115362 A CN96115362 A CN 96115362A CN 1067603 C CN1067603 C CN 1067603C
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- molecular sieve
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- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The present invention relates to a metallic modified SAPO-34 type molecular sieve catalyst converting methanol or dimethyl ether to low-carbon alkene. The modified metallic element adopts Cu, Co, Ni, Ca, Ba or Sr, an adhesive and a pore forming agent are added, and the adding quantity of the adhesive and the pore forming agent is respectively from 30 to 80% and from 1 to 15% of the weight of the catalyst. In the catalyst, modified metallic ions are introduced by a dipping technique during or after the synthesis of a molecular sieve. Used for the conversion reaction of the methanol or the dimethyl ether to the low-carbon alkene, and the catalyst has high activity (the conversion rate is close to 100%); the product low-carbon alkene, particularly ethene, has high selectivity; the catalyst can be repeatedly used by regeneration.
Description
The present invention relates to a kind ofly be raw material high selectivity system synthesizing ethylene by dimethyl ether or methyl alcohol, the modified small-porosity SAPO-34 type molecular sieve catalyst of low-carbon alkenes such as propylene reaction usefulness, its preparation method and be used for ethene with this catalyst, low-carbon alkenes such as propylene synthetic.
Second, propylene hydrocarbon are two kinds of quality maximums of petrochemical industry and a lot of basic material of purposes, be described as the mother of modern organic synthesis industry, the many industrially developed country in the world are all in the production technology of competing to develop this respect mutually, but what obtain them so far still mainly is the light oil cracking industrial process of traditional crude oil material.The impact of twice oil crisis of the seventies has advanced non-petroleum route to produce the paper carbon olefin or Fuel Petroleum is called C
1The development and research of chemistry, and formed international C at that time
1The chemical research upsurge.It is the most representative in working in this respect that to be U.S. Mobil company be raw material by methyl alcohol and be two kinds of new technology processes producing low-carbon alkene (MTO) and gasoline (MTG) respectively of catalyst with the ZSM-5 zeolite at middle nineteen seventies, occurred again subsequently with erionite, offretite, modenite, ZSM-34 or ZSM-45 are as the trial of MTO process catalyst; Developing pinhole phosphorus-silicon-aluminum SAPO-34 molecular sieve in the eighties U.S. combinating carbide in mid-term company (U.C.C) is active matrix sun MTO process a new generation catalyst, these catalyst performance characteristics double when being the comparable mesopore ZSM-5 of its ethylene selectivity catalyst, reach 50～60%.The applicant is once in proposed a kind ofly to produce new reaction technology (the claim SDTO) process of low-carbon alkene, Chinese patent publication number CN1067878A by the synthesis gas hydrocarbon by dimethyl ether in the early 1990s.Propose the preparation method of the used SAPO-34 molecular sieve catalyst of a series of these new technologies subsequently again and be used for methyl alcohol or dimethyl ether conversion is the technology of low-carbon alkene reaction.Chinese patent publication number CN1087292A, CN1096496A and CN1106715A.The raw materials used source of the method for preparing the SAPO-34 molecular sieve that above-mentioned technology provided is abundant, and is cheap, and catalyst has the selectivity of very high conversion ratio and low-carbon alkene to methyl alcohol and dimethyl ether conversion reaction, can be used for industrial production.But and mesopore ZSM-5 zeolite facies ratio, though the existing higher selectivity to low-carbon alkene because of its surface acidity is still very unsuitable, was also carried out the upgrading adjustment when aperture SAPO-34 molecular sieve was used for the MTO process, further improve low-carbon alkene, particularly to selectivity of ethylene.
The purpose of this invention is to provide a kind of to methyl alcohol or/and dimethyl ether conversion becomes low-carbon alkene reaction high catalytic activity to be arranged and product is had high selectivity, particularly ethene is had the very aperture SAPO-34 molecular sieve catalyst of high selectivity.
For realizing purpose of the present invention, the present inventor is further research with keen determination on the basis of previous work, one place's improvement project is proposed, at first by introducing different metal ions in the building-up process, such as two valency cation Cu, Co or Ni, alkaline-earth metal ions Ca particularly, the ion of Ba or Sr metal, the content of metal ion be molecular sieve heavy 0.01～0.15%, be preferably in 0.05～0.1%.The introducing of these metal cations not only can be regulated surface enzyme, also can change the aperture size of SAPO-34 molecular sieve, reaches the purpose of improving ethylene selectivity.Upgrading for the SAPO-34 molecule is handled, and also can carry out after it is synthetic, can above-mentioned metal ion be introduced by ion-exchange or slaine impregnation method.Can will further adjust in addition with hydrothermal treatment consists means under 700～800 ℃ of conditions.By above upgrading way, not only can adjust acidity, modify the aperture size, also can stablize the effect of SAPO-34 framework of molecular sieve.
Secondly, zeolite molecular sieve must add certain binding agent because himself adhesive property is poor, improves the mechanical strength of catalyst, reaches practical requirement, and suitable binding agent should be a weak acid, alkalescence, and neutral oxide material preferably is as SiP
2, Al
2O
3, TiO
2, MgO, CaO and their mixture etc.Their addition is 30 heavy～80%wt of molecular sieve.In addition, also should add certain organic matter pore creating material simultaneously, catalyst be carried out the purpose that secondary selects the hole to reach, can be as the carboxymethyl cellulose that mainly contains of pore creating material, starch and sesbania powder material, the consumption of pore creating material are 1～15%wt of catalyst.Specifically, the preparation process of cave of the present invention agent is: 1. synthetic SAPO-34 molecular sieve: its method technology is routinely carried out, and also can utilize commodity SAPO-34 molecular sieve.
2. introducing metal ion:
A. in synthetic SAPO-34 molecular sieve, add the soluble-salt solution of metal ion simultaneously,, metal cation is introduced in the molecular sieve as nitrate;
B utilizes dipping technique, with the soluble-salt solution of metal ion, as nitrate dipping SAPO-34 molecular sieve;
3. Preparation of catalysts
Utilize 2 material, make product catalyst after adding a certain amount of binding agent and changing hole agent aftershaping drying and roasting, drying is carried out under 50～120 ℃, and roasting was carried out under 350～650 ℃ 1～8 hour.
Above-mentioned catalyst is used for methyl alcohol or/and dimethyl ether conversion is the low-carbon alkene reaction, its reaction condition is: reaction temperature is: 500～600 ℃, optimum temperature is 530～570 ℃, and reaction pressure is a normal pressure, optimum pressure power is 0.01～10.05MPa, and reaction-ure feeding heavy burder air speed is 1～100h
-1, the best is 4～10h
-1Can carry out coke burning regeneration behind the catalysqt deactivation, its condition is: 550～650 ℃ of regeneration temperatures, the best are 590～610 ℃, and 5～30 minutes recovery times, the best is 8～12 minutes, available air, and nitrogen and air or the air that contains saturated vapor carry out.Below by embodiment technology of the present invention is given to illustrate further.
The preparation of embodiment 1 SAPO-34 molecular sieve
With the solution of 86.4 gram orthophosphoric acid and 165 gram deionized waters, restrain the solution of deionized waters successively with 109.8 gram pseudobochmites (water content 31.7%) and 100, and (contain SiO with 333.5 gram Ludox
2After 26.45%wt) 58.8 gram NaOH and 21.1 solution that restrain deionized waters mix, in above-mentioned mixture, add 78.0 gram triethylamines and 21.1 gram deionized waters again, stir 3 hours to even, in the stainless steel synthesis reactor of packing into.At room temperature aging 48 hours, again 200 ℃ of following crystallization 50 hours.Product washs and oven dry (120 ℃, 24 hours) after filtration.It is pure SAPO-34 molecular sieve that the x-ray powder diffraction is demonstrate,proved this product.
Embodiment 2 introduces the preparation of the SAPO-34 molecular sieve of modification agent
By the SAPO-34 molecular screen primary powder that obtains among the embodiment 1, through 350 ℃ 2 hours, 450 ℃ 2 hours, after 550 ℃ of roastings in 3 hours, get 25 grams, placing 250ml concentration is 10% calcium nitrate aqueous solution, under 80 ℃ of conditions, stir hour, the elimination redundant solution, 110 ℃ of oven dry 24 hours and 550 ℃ of roastings 4 hours promptly get the SAPO-34 molecular sieve of calcic.(contain Ca in the finished product
++Amount is for 0.05%wt) surface acid of the molecular sieve of this moment strong become had newly than prototype and weakened (TPD deamination method shows, the acid amount of upgrading rear catalyst be prototype SAPO-34 molecular sieve catalyst about 50%).And heat endurance is existing to be strengthened, framework of molecular sieve destroy the peak temperature by 1060～1100 ℃ of prototype rise to behind the upgrading more than 1200 ℃.
Embodiment 3 Preparation of catalysts
Get molecular sieve 25 grams that example 2 makes toward wherein adding Ludox (SiO wherein
2Content 26.5%wt) 94.4 grams, add simultaneously 2 gram sesbania powder again, material is stirred, carrying out the spray shaping operation on the spray drying device and under 150 ℃ of conditions again, make the microspheric that average particle becomes 40～60 μ m and become catalyst C, the heapization of this catalyst heavily is 0.62g/cm
3, at room temperature continuous 2000 hours cold conditions impact grinding loss rate＜20%wt.Repeat said method, do not prepare catalyst D but do not add the sesbania powder.Its pore structure is listed in the table below 1.
Table 1 pore creating material is to the influence of pore structure
| Sample | Pore creating material addition wt% | BETU surface m 2/g | Pore volume ml/g | Micro pore volume ml/g | Average pore size A ° |
| C D | 8 0 | 267.52 175.07 | 0.2223 0.3326 | 0.0908 0.0278 | 25.06 54.64 |
The performance of embodiment 4 catalyst
Methanol conversion is the low-carbon alkene reaction, adopt fixed-bed catalytic reactor, reactor is a quartz glass tube, loaded catalyst is 1.28 grams, the reaction procatalyst is warming up to 550 ℃ of activation 1 hour in the nitrogen stream of 60ml, reaction raw materials is carried by nitrogen and enters reactor, and the methyl alcohol molar content is 35% in the reactor feed gas, methyl alcohol weight space velocity WHSV2h
-1, reaction pressure is 0.05MPa, and reaction temperature is to react 1 hour under 400 ℃ of conditions, and branch cooked food sieve A, the B of use-case 1,2 preparation are catalyst respectively, and its reaction result is listed in table 2.
Table 2
| Catalyst | Methanol conversion (%) | C 2 -Selectivity (%) | C 3 -～C 3 -Selectivity (%) |
| A | 100 | 40.77 | 45.33 |
| B | 100 | 49.03 | 41.53 |
The performance 2 of embodiment 5 catalyst
Adopt fluidized bed reaction, fluidized reactor is the quartz glass material, the SAPO-34 molecular sieve catalyst C that provides with embodiment 3 under 600 ℃ of conditions with water vapour place 24 hours, be typing catalyst E, catalyst E15ml (about 10 grams) be seated in go into methyl alcohol with infusion in the fluidized reactor or dimethyl ether is a reaction raw materials.Before formal reaction test with purity nitrogen 550 ℃ of activation processing catalyst E1 hour, switch then and advance methyl alcohol or dimethyl ether, be converted into the reaction of low-carbon alkene, at 550 ℃ of reaction temperatures and methyl alcohol weight space velocity 6.45h
-1(or dimethyl ether weight space velocity 7.16h
-1) reaction 10 minutes the results are shown in following table 3 under the condition.
Table 2
| Reaction raw materials | Hydrocarbon product is formed %wt | |||
| CH 4 | C 2H 4 | C 3H 6 | C 2 -～C 4 - | |
| Methyl alcohol | 6.33 _ | 62.79 | 22.34 | 89.57 |
| Dimethyl ether | 6.42 | 59.35 | 24.22 | 88.32 |
The performance 3 of embodiment 6 catalyst
Adopting the foregoing description 5 identical fluidized bed reactions and catalyst E, is reaction raw materials with methyl alcohol, changes reaction temperature and methanol feeding weight space velocity, carried out respectively 10 minutes, it the results are shown in table 4, and under all reaction conditions, conversion of methanol is 100%.
Table 4
| Reaction condition | Hydrocarbon product is formed %wt | ||||
| Temperature ℃ | Methyl alcohol weight space velocity h-1 | CH 4 | C 2H 4 | C 4H 4 | C 2 -～C 4 - |
| 450 | 5.0 | 2. 0 | 31.0 | 38.2 | 78.4 |
| 490 | 5.0 | 3.0 | 35.4 | 36.3 | 83.2 |
| 530 | 5.0 | 4.4 | 45.6 | 30.5 | 87.8 |
| 5.0 | 5.0 | 6.3 | 52.4 | 23.4 | 89.0 |
| 570 | 5.0 | 9.8 | 60.3 | 22.1 | 87.3 |
| 550 | 3.0 | 6.5 | 51.2 | 28.5 | 88.3 |
| 550 | 6.0 | 6.2 | 58.1 | 23.2 | 89.5 |
| 55 | 10.0 | 6.0 | 62.3 | 20.0 | 90.2 |
Proper range of reaction temperature is 530～550 ℃, and relatively more suitable methyl alcohol weight space velocity scope 5.0～10.0h
-1
The test of embodiment 7 catalyst regenerations
Adopting the foregoing description 5 identical fluidized bed reactions and catalyst E, is raw material with the dimethyl ether, and reaction and catalyst regeneration that this catalyst E carries out are repeatedly tested.Regeneration test shows in 550～650 ℃ of temperature ranges, can directly burn with air.When used regeneration temperature is hanged down. the time of burning is long, otherwise then can shorten, all the burn off coke with make the catalyst activity recovery.As burning 550 ℃ the time, regeneration can be finished in 30～40 minutes, then can finish within 5 minutes in the time of 650 ℃.But the suitable regeneration condition of burning is 600 ℃, and under 10 minutes and the air, it the results are shown in table 5.
Table 5 carries out the result of the test of 100 regeneration continuously
| Regeneration times 8 | 0 | 10 | 30 | 60 | 80 | 100 |
| Reaction temperature ℃ | 550 | 530 | 530 | 530 | 530 | 530 |
| Olefine selective %wt | ||||||
| C 2 -Selectivity (%) | 35.66 | 49.49 | 52.55 | 52.53 | 52.33 | 50.69 |
| C 3 -Selectivity (%) | 39.76 | 34.09 | 34.45 | 31.45 | 32.08 | 35.88 |
| C 3 -～C 4 -Selectivity (%) | 11.16 | 92.19 | 94.31 | 92.51 | 92.66 | 93.46 |
Reaction condition: dimethyl ether weight space velocity 2.0h
-1
Dimethyl ether conversion rate～100%.
Claims (4)
- Methyl alcohol or dimethyl ether conversion be low-carbon alkene with metal-modified SAPO-34 type molecular sieve catalyst, it is characterized in that modified metal element Cu, Co, Ni, Ca, Ba or Sr, the content of metallic element be molecular sieve weight O.01～O.15%.
- 2. according to the described catalyst of claim 1, it is characterized in that adding binding agent and pore creating material, its addition be respectively catalyst heavy 30～80% and 1～15%; So-called binding agent is SiO 2, Al 2O 3Or one or both mixtures among the MgO, so-called pore creating material is sesbania powder, carboxymethyl cellulose or starch.
- 3. according to claim 1,2 described catalyst is characterized in that the modified metal element is Ca, and used binding agent is SiO 2, used pore creating material is the sesbania powder.
- 4. one kind according to the described Preparation of catalysts method of claim 1, it is characterized in that pressing step:1) technology is synthesized SAPO-34 type molecular sieve or is directly got commodity SAPO-34 type molecular sieve and make material routinely;2) introduce the modified metal ionA. in synthetic SAPO-34 molecular sieve, add the soluble-salt solution of metal ion simultaneously, metal cation is introduced in the molecular sieve;Or b, utilize dipping technique, with the soluble-salt solution of metal ion, as nitrate dipping SAPO-34 molecular sieve;3) Preparation of catalystsUtilize 2) material, make product catalyst after adding a certain amount of binding agent and changing hole agent aftershaping drying and roasting, dry under 50～120 ℃, carry out, roasting was carried out under 350～650 ℃ 1～8 hour.
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| CN96115362A CN1067603C (en) | 1996-06-07 | 1996-06-07 | Metal modified small-porosity P-Si-Al molecular sieve catalyst, its preparing process and use thereof |
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| CN96115362A CN1067603C (en) | 1996-06-07 | 1996-06-07 | Metal modified small-porosity P-Si-Al molecular sieve catalyst, its preparing process and use thereof |
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| CN1067603C true CN1067603C (en) | 2001-06-27 |
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Cited By (2)
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|---|---|---|---|---|
| CN108203102A (en) * | 2016-12-16 | 2018-06-26 | 中国石油天然气股份有限公司 | Composite modified SAPO-34 molecular sieve and preparation method thereof |
| US10259757B2 (en) | 2006-08-23 | 2019-04-16 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Method for starting up a fluidized catalytic reaction apparatus used for producing lower olefins |
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| CN100368086C (en) * | 2004-04-16 | 2008-02-13 | 中国石油化工股份有限公司 | Synthetic method for metal ion containing silicon-phosphor-aluminium molecular shieve |
| CN100377784C (en) * | 2004-09-28 | 2008-04-02 | 中国石油化工股份有限公司 | Metal modified SAPO-34 molecular screen and its uses |
| CN1332761C (en) * | 2005-07-13 | 2007-08-22 | 清华大学 | Process for preparing load type silicon phoshporus aluminium molecular sieve |
| US20070037692A1 (en) * | 2005-08-10 | 2007-02-15 | Beech James H Jr | Method for stabilizing catalyst activity during MTO unit operation |
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| CN101157594B (en) * | 2007-06-14 | 2011-07-20 | 中国科学院大连化学物理研究所 | Reaction performance appraising method of fluidized bed catalyst during preparation of light olefins by methanol |
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| CN105984876B (en) * | 2015-01-30 | 2018-06-29 | 中国科学院大连化学物理研究所 | A kind of preparation method of metal-modified SAPO molecular sieve |
| CN107597180A (en) * | 2017-08-31 | 2018-01-19 | 江苏有容催化技术研究所有限公司 | Novel carbinol alkene catalyst preparation method |
| CN111250155B (en) * | 2020-03-03 | 2021-09-24 | 清华大学 | Molecular sieve catalyst with double active centers and preparation and application thereof |
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| US10259757B2 (en) | 2006-08-23 | 2019-04-16 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Method for starting up a fluidized catalytic reaction apparatus used for producing lower olefins |
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| CN108203102B (en) * | 2016-12-16 | 2019-11-08 | 中国石油天然气股份有限公司 | Composite modified SAPO-34 molecular sieve and preparation method thereof |
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Assignee: Chia Tai Energy Materials (Dalian) Co., Ltd. Assignor: Dalian Institute of Chemical Physics, Chinese Academy of Sciences Contract record no.: 2010990000644 Denomination of invention: Metal modified small-porosity P-Si-Al molecular sieve catalyst, its preparing process and use thereof Granted publication date: 20010627 License type: Exclusive License Open date: 19971217 Record date: 20100813 |
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