CN1704390A - Method for preparing olefin by conversion of methanol - Google Patents
Method for preparing olefin by conversion of methanol Download PDFInfo
- Publication number
- CN1704390A CN1704390A CNA200410024734XA CN200410024734A CN1704390A CN 1704390 A CN1704390 A CN 1704390A CN A200410024734X A CNA200410024734X A CN A200410024734XA CN 200410024734 A CN200410024734 A CN 200410024734A CN 1704390 A CN1704390 A CN 1704390A
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- China
- Prior art keywords
- conversion system
- methanol conversion
- molecular sieve
- reaction
- sapo
- Prior art date
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Links
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 119
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 21
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 19
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title abstract 2
- 239000002808 molecular sieve Substances 0.000 claims abstract description 24
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 24
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 17
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 229910001868 water Inorganic materials 0.000 claims description 16
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 15
- 239000011230 binding agent Substances 0.000 claims description 8
- 238000002425 crystallisation Methods 0.000 claims description 7
- 230000008025 crystallization Effects 0.000 claims description 7
- 239000011701 zinc Substances 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229960004217 benzyl alcohol Drugs 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 150000003751 zinc Chemical class 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 11
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 239000007767 bonding agent Substances 0.000 abstract 1
- -1 carbon alkene Chemical class 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 239000004411 aluminium Substances 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 241000219782 Sesbania Species 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- BQJCRHHNABKAKU-KBQPJGBKSA-N morphine Chemical compound O([C@H]1[C@H](C=C[C@H]23)O)C4=C5[C@@]12CCN(C)[C@@H]3CC5=CC=C4O BQJCRHHNABKAKU-KBQPJGBKSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- 229910017090 AlO 2 Inorganic materials 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical class O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- GHTGICGKYCGOSY-UHFFFAOYSA-K aluminum silicon(4+) phosphate Chemical compound [Al+3].P(=O)([O-])([O-])[O-].[Si+4] GHTGICGKYCGOSY-UHFFFAOYSA-K 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- UNYSKUBLZGJSLV-UHFFFAOYSA-L calcium;1,3,5,2,4,6$l^{2}-trioxadisilaluminane 2,4-dioxide;dihydroxide;hexahydrate Chemical compound O.O.O.O.O.O.[OH-].[OH-].[Ca+2].O=[Si]1O[Al]O[Si](=O)O1.O=[Si]1O[Al]O[Si](=O)O1 UNYSKUBLZGJSLV-UHFFFAOYSA-L 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 229910052676 chabazite Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 235000011194 food seasoning agent Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229960005181 morphine Drugs 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
-
- 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
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for preparing olefin by conversion of methanol by using Zn-SAPO-34 molecular sieve and bonding agent as the catalyst for alkene production through methanol converstion, and employing a reaction temperature of 300-500 deg. C, a reaction pressure of atmospheric pressure, methanol weight space velocity of 1.0-10hr-1, the prepared low carbon alkene can be used in the industrial production of alkene from methanol.
Description
Technical field
The method of the methanol conversion system of the present invention relates to alkene is particularly about the method for methanol conversion system ethene, propylene.
Background technology
Ethene, the effect of propylene in modern chemistry industry hold the balance.Up to this point, most ethene, propylene all come from refining of petroleum.But for oil, price increase and supply problem of unstable were arranged in short duration, then have the resource storage capacity limited for a long time, thereby produce the problem of " oil crisis ".By methyl alcohol or dme is that to produce low-carbon alkene (MTO or DTO) be the novel process that is hopeful to replace petroleum path most to catalytic material.The synthesis technique of methyl alcohol, dme is quite ripe, and raw material sources are abundant, such as coal, Sweet natural gas and solid waste being passed through synthetic gas (CO+H
2) directly synthetic obtaining.For this novel process, appropriate catalyst is a key point.In U.S. Pat 4440871, U.S. carbon compound company (UCC) has developed novel silicon aluminium phosphate series molecular sieve (SAPO-n).Wherein SAPO-34 has represented the catalytic performance preferable to MTO.Synthesized silicon-aluminum phosphate SAPO-34 molecular sieve is by SiO
2, AlO
2 -, PO
2 +Three kinds of tetrahedrons interconnect and form, and have structure, window diameter range 0.43～0.50 nanometer of class chabazite, and have moderate acid and good thermostability and hydrothermal stability.The catalyzer that with the SAPO-34 molecular sieve is active ingredient is to MTO or DTO) reaction has than excellent catalytic performance, and its initial conversion can reach 100%, and (ethene+propylene) selectivity can reach more than 80%.According to the present requirement of China, therefore the demand growth of propylene can reach ethene in MTO or the DTO product, the adjustable relatively requirement of propylene ratio by regulating processing condition greater than the demand growth of ethene.
Summary of the invention
Technical problem to be solved by this invention is to use in the document to exist ethene, propylene selectivity low in the aluminium silicophosphate molecular sieve producing light olefins technology in the past, and ethene, the problem that propene yield is low provide a kind of method of new methanol conversion system alkene.When this method is used for methanol to olefins reaction, have ethene, propylene selectivity height, the characteristics that yield is high.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method of methanol conversion system alkene is a raw material with methyl alcohol, and water is solvent, is 300～500 ℃ in temperature of reaction, and reaction pressure is a normal pressure, and the weight space velocity of methyl alcohol is 1.0～10 hours
-1, water/methyl alcohol weight ratio is under 0～5 condition, and material benzenemethanol reacts by beds and generates ethene and propylene, and wherein catalyzer comprises following component by weight percentage:
A) 10～100% Zn-SAPO-34 molecular sieve;
B) 0～90% binding agent.
In the technique scheme, the temperature of reaction preferable range is 400～500 ℃, and the weight space velocity preferable range of methyl alcohol is 1.0～5 hours
-1, water/methyl alcohol weight ratio preferable range is 3～5.By weight percentage, the amount preferable range of Zn-SAPO-34 molecular sieve is 30～80%; Binding agent consumption preferable range is 20～70%, and the binding agent preferred version is to be selected from least a in aluminum oxide, silicon oxide or the magnesium oxide, and more preferably scheme is an aluminum oxide.Zinc preferred version in the Zn-SAPO-34 molecular sieve is directly to add the synthetic SAPO-34 of introducing framework of molecular sieve in the crystallization liquid by zinc salt.
Preparation of catalysts process of the present invention is described below:
1. the synthetic SAPO-34 molecular screen primary powder that contains Zn.During molecular sieve synthetic, its silicon source can be silicon sol, active silica or tetraethoxy, and the aluminium source can be pseudo-boehmite, alcoxyl aluminium or activated alumina.The raw material of template, silicon source, aluminium source, phosphorus source and water meets following formula: 0.03～0.6R: (Si
0.01～0.98: Al
0.01～0.6: P
0.01～06): 2～500H
2O: 0.03～0.6M
M represents Zn salt, and R represents template, can adopt tetraethyl ammonium hydroxide, morpholine, triethylamine or their mixture etc. as template.
Concrete molecular sieve preparation method carries out according to the following steps:
1), takes by weighing a certain amount of silicon source, phosphorus source, aluminium source, water, template, metal-salt according to the proportioning in the said structure formula
2) according to a definite sequence with the mixing of materials that weighs up, and stir the formation gel fully
3) with 2) resulting gel 100～250 ℃ of following crystallization again, the reaction times, the solid that the product behind the crystallization filters and centrifugation obtains was through the SAPO-34 molecular screen primary powder of washing, drying can obtain containing Zn greater than 0.5 hour.Its drying can seasoning or 80 ℃ again～150 ℃ under carry out.
2. Preparation of catalysts.Utilize the SAPO-34 molecular screen primary powder of the 1 resulting Zn of containing, add that drying and roasting make product catalyst behind a certain amount of binding agent and the pore-forming material, drying is carried out under 50～120 ℃, roasting was carried out under 350～600 ℃ 1～8 hour, and wherein pore-forming material is selected from sesbania powder, carboxymethyl cellulose or starch.
When above-mentioned catalyzer is used for the reaction of methanol-to-olefins reaction, temperature of reaction is 300～500 ℃, reaction pressure is a normal pressure, preferable temperature of reaction is 400～500 ℃, the weight space velocity of methyl alcohol was at 1.0～5.0 o'clock, conversion of raw material can reach 100%, utilizes the yield of low-carbon alkene of the molecular sieve catalyst that the present invention makes higher.
The present invention is owing to adopt the catalyst activity component of Zn-SAPO-34 molecular sieve as methanol conversion system alkene, its catalyst performance has had obvious improvement than Hydrogen SAPO-34 molecular sieve, simultaneously by regulating water/alcohol ratio, the temperature of reaction condition, the selectivity of ethene, propylene and butylene is significantly improved, can reach 96.86%, the yield of ethene and propylene can reach more than 91% simultaneously, has obtained better technical effect.
The invention will be further elaborated below by embodiment.
Embodiment
[embodiment 1]
Synthesizing of the SAPO-34 molecular sieve of containing metal Zn
According to formula (0.5TEAOH+2.0Morpholine): 0.6SiO
2: Al
2O
3: P
2O
5: 60H
2O: 0.03Zn (NO
3)
2Take by weighing raw material.
Earlier with a certain amount of rAl
2O
3H2O, positive acid solution fully mix and form the homogeneous jelly.Keep whipped state, add the composite mould plate agent that zinc nitrate aqueous solution, silicon sol, tetraethyl ammonium hydroxide and morphine quinoline are formed successively, mend a certain amount of deionized water at last.Fully stir the back and form the crystallization mixed solution.With the crystallization mixed solution that obtains above 200 ℃ of following crystallization 48 hours, product obtains solid phase prod after centrifugation, it 110 ℃ of oven dry in baking oven is spent the night, the XRD test shows, products obtained therefrom is the SAPO-34 molecular sieve, and do not have other impurity peaks, illustrate that metal ion has entered the skeleton of molecular sieve equably.
[embodiment 2]
Molecular sieve catalyst preparation 1
The former powder that makes in the example 1 was removed template in 3.0 hours 600 ℃ of following roastings, carry out compressing tablet respectively, broken back sieve is got 20-40 purpose granularity part, is numbered CS-01, wait to check and rate.
[embodiment 3]
Molecular sieve catalyst preparation 2
Get former powder 6 grams that make in the example 1, with rAl
2O
3H
2O 6 gram, sesbania powder 2 grams mix, and add the rare nitric acid 9ml of 3wt%, mediate, extruded moulding, 120 ℃ of dry down 8 hours, 600 ℃ following roastings 3.0 hours, and broken back sieve is got 20-40 purpose granularity part, is numbered CS-02, waits to check and rate.
[embodiment 4]
The molecular sieve catalyst examination
Adopt fixed-bed catalytic reactor, embodiment 1 and embodiment 2 resulting CS-01, CS-02 catalyzer are carried out catalyzer examination experiment respectively.Experiment condition is, the catalyzer loading capacity is 1.46 grams, and temperature of reaction is 450 ℃, and reaction pressure is a normal pressure, and the weight space velocity of first alcohol and water was respectively 1.25 hours
-1With 3.75 hours
-1, the flow of nitrogen is 50 ml/min.The results are shown in Table 1.
The result of table 1 methanol-to-olefins reaction
| Sample | Methanol conversion (weight %) | Reaction times *(hour) | Hydrocarbon product distribution (weight %) | ||||||||
| ??CH 4 | ??C 2H 6 | ??C 2H 4 | ??C 3H 8 | ??C 3H 6 | ??C 4H 10 | ??C 4H 8 | ??C 5 + | ??C 2 ＝～C 4 ＝ | |||
| ?CS-01 | ????100％ | ????6.0 | ??1.38 | ??0.39 | ??60.12 | ??0.40 | ??31.22 | ??0 | ??5.52 | ??0.97 | ??96.86 |
| ?CS-02 | ????100％ | ????6.0 | ??2.54 | ??0.45 | ??57.49 | ??0.44 | ??30.89 | ??0 | ??6.12 | ??2.07 | ??94.50 |
*Reaction times is defined as before the dme appearance, and the oxygenate rate is 100% time
[embodiment 5]
Change the experiment of feed water alcohol ratio
Experiment condition is: the catalyzer loading capacity of getting embodiment 4 is 1.46 grams, and temperature of reaction is 450 ℃, and reaction pressure is a normal pressure, and the weight space velocity of methyl alcohol is 10 hours
-1, the flow of nitrogen is 50 ml/min.The results are shown in Table 1.As can be seen from the table, water alcohol is than being 0.1,3 or 5 o'clock, and the selectivity situation of the initial conversion of methyl alcohol, (ethene+propylene) sees Table 2.
The result of table 2 methanol-to-olefins reaction
| Methanol conversion (weight %) | Water alcohol is than (gram/gram) | Products distribution (weight %) | |||||||||
| ?CH 4 | ??C 2H 6 | ?C 2H 4 | ??C 3H 8 | ??C 3H 6 | ??C 4H 10 | ??C 4H 8 | ??C 5 + | ??DME | ??MEOH | ||
| ??100％ | ??0 | ?1.40 | ??0.43 | ?36.63 | ??1.84 | ??33.14 | ????0 | ??12.66 | ??3.91 | ??0.36 | ??9.63 |
| ??100％ | ??1 | ?0.75 | ??0 | ?45.85 | ??0 | ??37.13 | ????0 | ??10.52 | ??2.51 | ??0.38 | ??2.86 |
| ??100％ | ??3 | ?0.85 | ??0 | ?46.15 | ??0 | ??36.80 | ????0 | ??10.84 | ??2.58 | ??0.44 | ??2.34 |
| ??100％ | ??5 | ?0.84 | ??0 | ?46.39 | ??0 | ??35.56 | ????0 | ??10.42 | ??2.36 | ??0.59 | ??3.84 |
*15 minutes sample times
[embodiment 6]
Change the experiment of temperature of reaction
Experiment condition is: the catalyzer loading capacity of getting embodiment 4 is 1.46 grams, and temperature of reaction is 400 ℃, and 450 ℃, 500 ℃, reaction pressure is a normal pressure, and the weight space velocity of first alcohol and water was respectively 10 hours
-1With 30 hours
-1, the flow of nitrogen is 50 ml/min, the results are shown in Table 3.As can be seen from the table, the relative proportion of ethene, propylene can be regulated easily by temperature of reaction.
The result of table 3 methanol-to-olefins reaction
| Methanol conversion (weight %) | Temperature of reaction (℃) | Products distribution (weight %) | |||||||||
| ??CH 4 | ??C 2H 6 | ??C 2H 4 | ??C 3H 8 | ??C 3H 6 | ?C 4H 10 | ??C 4H 8 | ??C 5 + | ??DME | ??MEOH | ||
| ????100％ | ????400 | ??0.52 | ??0.43 | ??36.28 | ??0 | ??42.53 | ??0 | ??14.74 | ??2.96 | ??0.34 | ??2.63 |
| ????100％ | ????450 | ??0.85 | ??0 | ??46.15 | ??0 | ??36.80 | ??0 | ??10.84 | ??2.58 | ??0.44 | ??2.34 |
| ????100％ | ????500 | ??2.73 | ??0 | ??52.61 | ??0 | ??27.73 | ??0 | ??7.44 | ??2.34 | ??1.19 | ??5.96 |
*15 minutes sample times
[embodiment 7]
Experiment condition is: the catalyzer loading capacity of getting embodiment 4 is 1.46 grams, and temperature of reaction is 450 ℃, and reaction pressure is a normal pressure, and the weight space velocity of first alcohol and water was respectively 5 hours
-1With 15 hours
-1, the flow of nitrogen is 50 ml/min, and the result is as follows: methanol conversion is 100%, and the yield of (ethene+propylene) is 84.57%.
Claims (8)
1, a kind of method of methanol conversion system alkene is a raw material with methyl alcohol, and water is solvent, is 300～500 ℃ in temperature of reaction, and reaction pressure is a normal pressure, and the weight space velocity of methyl alcohol is 1.0～10 hours
-1, water/methyl alcohol weight ratio is under 0～5 condition, and material benzenemethanol reacts by beds and generates ethene and propylene, and wherein catalyzer comprises following component by weight percentage:
A) 10～100% Zn-SAPO-34 molecular sieve;
B) 0～90% binding agent.
2,, it is characterized in that temperature of reaction is 400～500 ℃ according to the method for the described methanol conversion system alkene of claim 1.
3, according to the method for the described methanol conversion system alkene of claim 1, the weight space velocity that it is characterized in that methyl alcohol is 1.0～5 hours
-1
4,, it is characterized in that water/methyl alcohol weight ratio is 3～5 according to the method for the described methanol conversion system alkene of claim 1.
5, according to the method for the described methanol conversion system alkene of claim 1, it is characterized in that by weight percentage the amount of Zn-SAPO-34 molecular sieve is 30～80%, the binding agent consumption is 20～70%.
6,, it is characterized in that binding agent is selected from least a in aluminum oxide, silicon oxide or the magnesium oxide according to the method for the described methanol conversion system alkene of claim 1.
7,, it is characterized in that binding agent is an aluminum oxide according to the method for the described methanol conversion system alkene of claim 6.
8,, it is characterized in that the zinc in the Zn-SAPO-34 molecular sieve is directly to add the synthetic SAPO-34 of introducing framework of molecular sieve in the crystallization liquid by zinc salt according to the method for the described methanol conversion system alkene of claim 1.
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| CN102372539A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Method for producing low-carbon olefin |
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Application publication date: 20051207 Assignee: Sinopec Nanjing Catalyst Co.,Ltd. Assignor: SHANGHAI Research Institute OF PETROCHEMICAL TECHNOLOGY SINOPEC Contract record no.: X2023310000030 Denomination of invention: Methods of methanol conversion to olefins Granted publication date: 20060809 License type: Common License Record date: 20230316 |
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