CN103980083A - Method for preparing propylene from methanol - Google Patents
Method for preparing propylene from methanol Download PDFInfo
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- CN103980083A CN103980083A CN201410219103.7A CN201410219103A CN103980083A CN 103980083 A CN103980083 A CN 103980083A CN 201410219103 A CN201410219103 A CN 201410219103A CN 103980083 A CN103980083 A CN 103980083A
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 126
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 32
- 239000003054 catalyst Substances 0.000 claims abstract description 55
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000011049 filling Methods 0.000 claims abstract description 21
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 20
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 19
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 7
- 239000002808 molecular sieve Substances 0.000 claims description 25
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 15
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims description 11
- 239000011574 phosphorus Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 230000004048 modification Effects 0.000 claims description 8
- 238000012986 modification Methods 0.000 claims description 8
- 239000010410 layer Substances 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 238000012856 packing Methods 0.000 claims description 6
- 239000011229 interlayer Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 5
- 150000001336 alkenes Chemical class 0.000 abstract description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 abstract description 3
- 238000007233 catalytic pyrolysis Methods 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 2
- 238000010517 secondary reaction Methods 0.000 abstract description 2
- 238000005899 aromatization reaction Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 40
- 239000000463 material Substances 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 8
- 239000012808 vapor phase Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 239000012263 liquid product Substances 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 2
- 238000009415 formwork Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000003915 liquefied petroleum gas Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000002253 acid 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
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000012962 cracking technique Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 235000021463 dry cake Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- -1 small molecules hydro carbons Chemical class 0.000 description 1
- 239000008279 sol Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a method for preparing propylene from methanol. The method comprises the step of utilizing a first reactor and a second reactor to carry out reaction for preparing propylene from methanol, wherein the first reactor is used for carrying out reaction for synthesizing dimethyl ether with methanol so as to obtain a first product flow; the second reactor is used for carrying out reaction for preparing propylene with the first product flow so as to obtain a second product flow; a plurality of catalyst bed layers are longitudinally arranged in the second reactor and are filled with first catalysts and second catalysts; the second product flow is separated to obtain circulating hydrocarbon product flows containing C2, C4, C5 and C6; and the circulating hydrocarbon product flows are sent into the second reactor again. By adopting the method, by filling two kinds of catalysts with different acidity in the reactors, the circulating hydrocarbon is partially subjected to catalytic pyrolysis on the catalyst bed layer with stronger acidity, meanwhile, secondary reactions undergone by olefin molecules, such as hydrogen transfer, aromatization and the like to generate alkane and macromolecular aromatic hydrocarbon are reduced and the yield of propylene is increased.
Description
Technical field
The invention belongs to preparing propylene from methanol field, particularly the filling of catalyzer and the method for reactor feed in a kind of preparing propylene from methanol.
Background technology
Ethene, propylene are all important petrochemical complex basic materials, and annual requirement is huge, and especially propylene is the second largest chemical of current global demand amount, and consumption significantly improves, and has even surpassed ethene.Up to this point, propylene still mainly comes from the light oil cracking/cracking technique in refining of petroleum, and obtains with co-product or by product mode, but along with the appearance of " oil crisis " problem, will certainly make propylene be very limited in raw material and output.For the energy structure of the rich coal of China, oil-poor, weak breath, the preparing propylene transformed technology of methanol oxidation has good application prospect and far-reaching strategic importance.
At present, technique report by preparing light olefins from methanol is more, mainly contain the preparing propylene from methanol technology (MTP) of German Lurgi company, the methanol-to-olefins technology (MTO) of American UOP company, the fluidized-bed preparing propylene from methanol technology (FMTP) that the methanol/dimethyl ether producing light olefins technology (DMTO) of domestic Dalian Chemiclophysics Inst., Chinese Academy of Sciences independent development and Tsing-Hua University develop.
Wherein, the MTP technology product of German Lurgi company be take propylene as main, and forms multinomial patented technology (CN1431982A, EP448000, WO20061364.33 etc.), is about to enter extensive industrialization.This technique is comprised of two sections of insulation fix bed reactors, i.e. and in I section dimethyl ether reactor (DME reactor), methanol steam is first at the Al of high reactivity, highly selective
2o
3catalyst based upper, under 200～400 ℃ of conditions, partial dehydration generates dme; Unreacted methyl alcohol and dme-water mixture continue to enter II section MTP reactor, in II section reactor under the catalyst based effect of ZSM-5, in 400～500 ℃ further reaction generate that to take propylene be main hydrocarbon mixture product, and with the generation of a large amount of ethene, gasoline and liquefied petroleum gas (LPG).For improving the total recovery of target product propylene, hydro carbons after separating ethene and propylene need be looped back to II section MTP reactor continues to transform, but this conversion reaction is very complicated, cause the catalyst based easy coking and deactivation of ZSM-5 in II section insulation fix bed reactor, need carry out original position super regeneration, cause reaction efficiency lower.
Summary of the invention
The object of the present invention is to provide a kind of method of preparing propylene from methanol, to improve propene yield, the extending catalyst life-span.
For achieving the above object, the present invention adopts following technique means:
A method for preparing propylene from methanol, comprises and utilizes the first reactor and the second reactor to carry out preparing propylene from methanol reaction; Wherein, described the first reactor is for methyl alcohol dimethyl ether synthesizing reaction, to obtain the first product stream; Described the first product stream comprises dme, water and unreacted methyl alcohol;
Described the second reactor is for the propylene reaction processed of described the first product stream, to obtain the second product stream; And be longitudinally provided with a plurality of beds in described the second reactor, on the beds of described the second reactor, be filled with the first catalyzer and the second catalyzer, described the first catalyzer is HZSM-5 molecular sieve catalyst, and described the second catalyzer is the catalyzer of HZSM-5 molecular sieve catalyst gained after metal load or phosphorus modification;
Described the second product stream is isolated to and comprises C
2, C
4, C
5and C
6the recycle hydrocarbons product stream of component, sends into described recycle hydrocarbons product stream in described the second reactor again.
Further describe the method for preparing propylene from methanol provided by the present invention below.
In the present invention, utilize the method for preparing propylene from methanol mainly to comprise two parts: the methyl alcohol dimethyl ether synthesizing reaction carrying out in the first reactor, and the reaction that utilizes the further synthesizing propylene of the first product stream in the second reactor.
According to the preferred embodiment of the present invention, in described the first reactor, be longitudinally provided with two beds; The methanol feeding of described the first reactor is divided into first burst of charging and second burst of charging; Wherein, described first burst of charging accounts for the 65wt%～85we% of described methanol feeding and is preheated to 260 ℃～300 ℃, further preferably, described first burst of charging accounts for the 70wt%～80wt% of described methanol feeding and is preheated to after 270 ℃～290 ℃, from the top of described the first reactor, enter, carry out the strong exothermal reaction of methanol dehydration dimethyl ether synthesis; Described second burst of charging for example, without preheating (described second strand of material keeps the temperature of 20 ℃～40 ℃), deliver between two beds of described the first reactor, mix with the reaction product of described first burst of charging, absorb above-mentioned strong exothermal reaction institute liberated heat, and proceed methyl alcohol dimethyl ether synthesizing reaction.Compare with traditional whole its top feed modes, method of the present invention can be controlled the temperature in described the first reactor better, and then extends the wherein work-ing life of catalyzer.
In the method for the invention, for raising productivity of propylene, described the second product stream is isolated to and comprises C
2, C
4, C
5and C
6the recycle hydrocarbons product stream of component, described recycle hydrocarbons product stream is sent into described the second reactor again, and described circulation products stream mainly carries out catalytic cracking reaction to generate propylene in described the second reactor.In order to guarantee efficiently carrying out of catalytic cracking reaction, at described the second catalyst reactor, should there is stronger acidity, such as HZSM-5 molecular sieve catalyst, so that recycle hydrocarbons product stream catalytic pyrolysis generates olefin product, improve target product yield; Yet, for the stronger catalyzer of acidity, easily there is hydrogen transfer reactions, the conversion of olefines that reaction is generated is a large amount of alkane.
For this reason, in the method for the invention, on described the second reactor catalyst bed, be filled with the first catalyzer and the second catalyzer: described the first catalyzer is HZSM-5 molecular sieve catalyst, preferably, described the first catalyzer is disclosed HZSM-5 molecular sieve catalyst in CN201210531577.6; Particularly, described the first catalyzer is prepared by the following method, comprising:
A, silicon source, aluminium source, organic formwork agent, alkali and deionized water are mixed with to mixture by weight 85.0～92.0:2.0～8.0:0.8～1.5:0～0.1:5.0～10.0;
B, the mixture of step a is evaporated 1～24 hour at the temperature of 70～100 ℃, make concentrated gel material;
C, concentrated gel material is moved in seal pot, at the temperature of 100～200 ℃, crystallization is 1～12 day, and the crystallization product in seal pot is carried out to chilling;
D, the product of step c gained is washed to filtrate pH=8～9, dry cake 450～600 ℃ of roastings 2～8 hours, obtains ZSM-5 molecular sieve;
E, acid solution or ammonium salt by ZSM-5 molecular sieve by 0.1～8.5 mol/L, at solvent and solute weight ratio, be 1～30:1, temperature is to carry out ion-exchange under 30～90 ℃ of conditions, and the roasting 2～8 hours at 450～600 ℃ of the filter cake after filtration, obtains HZSM-5 molecular sieve catalyst.
Wherein, described silicon source is one or more the mixture in silicon-dioxide, silicon sol, tetraethoxy, White Carbon black; Described aluminium source is one or more the mixture in Tai-Ace S 150, aluminum chloride, aluminum nitrate, sodium metaaluminate; Described organic formwork agent comprises one or more the mixture in TPAOH, 4-propyl bromide or triethylamine; Described alkali is selected from a kind of in sodium hydroxide or potassium hydroxide or two kinds.
Described the second catalyzer is the catalyzer that HZSM-5 molecular sieve catalyst obtains after metal load (also referred to as metal-modified) or phosphorus modification (modifying also referred to as phosphorus), to regulate the acidity of HZSM-5 molecular sieve catalyst.
HZSM-5 molecular sieve catalyst is carried out to the processing such as metal load or phosphorus modification and be catalyst treatment means known in the art.For example, when carrying out metal load, can be according to CN201110293745.8, CN200710040699.4, in the patents such as CN200710202215.1, disclosed method is carried out metal load to HZSM-5 molecular sieve catalyst, and the second catalyzer obtaining can be disclosed catalyzer in CN201110293745.8.
In the present invention, when HZSM-5 molecular sieve catalyst is carried out to phosphorus modification, can be according to CN201010296555.7, CN201280013077.1, in the patents such as CN201310172615.8, disclosed method is carried out phosphorus modification to HZSM-5 molecular sieve catalyst, and the second catalyzer obtaining can be disclosed catalyzer in CN201310172615.8.Preferably, the mass ratio of described the first catalyzer and the second catalyzer is 1:2～2:1.
According to the preferred embodiment of the present invention, described the second catalyzer is the catalyzer that HZSM-5 molecular sieve catalyst obtains after phosphorus modification; Further preferably, described the second catalyzer is disclosed Modified HZSM-5 Zeolite Catalyst in CN201310172615.8, and particularly, described the second catalyzer is prepared by the following method, comprising:
(1), HZSM-5 molecular sieve powder is added in the tackiness agent of silicon-aluminum sol, mix, moulding, in wherein said silicon-aluminum sol, silicon, aluminium are respectively with SiO
2and Al
2o
3the quality sum of meter is 10～30wt% of described HZSM-5 molecular sieve powder;
(2) product, step (1) being obtained obtains molded molecular sieve 400～600 ℃ of roastings;
(3), phosphorus source is dissolved in distilled water or ethanol to the solution containing phosphate that formation concentration is 1～5wt%;
(4), the molded molecular sieve that obtains of the solution containing phosphate treatment step (2) that obtains by step (3), then the molecular sieve after processing is obtained to catalyzer 400～600 ℃ of roastings.
Wherein, the silica alumina ratio SiO of described HZSM-5 molecular sieve
2/ Al
2o
3be 50～300.
Described phosphorus source is one or more the mixture in phosphoric acid, metaphosphoric acid, tetra-sodium, ammonium phosphate, ammonium hydrogen phosphate, primary ammonium phosphate and diethyl phosphite.
Further preferred embodiment of the present invention this, the mass ratio of described the first catalyzer and the second catalyzer is 1:1～2:1.
In the method for the invention, in described the second reactor, be longitudinally provided with a plurality of beds, such as 4-8, or 6; Described the first catalyzer and the second catalyst filling are to each beds of described the second reactor.In one embodiment of the invention, the filling mode of described the first catalyzer and the second catalyzer is: the mixture of described the first catalyzer mixing and the second catalyzer is loaded respectively to each beds to described the second reactor.This kind of filling mode is simple to operate, easy to implement.
In another embodiment of the invention, the filling mode of described the first catalyzer and the second catalyzer is: described the first catalyzer from the superiors of the beds of described the second reactor down interlayer load the corresponding catalyst bed to described the second reactor, described the second catalyst filling is to described remaining beds of the second reactor.Research is found, than by the extremely top whole fillings of beds, the second catalyzer beds extremely on the lower of the whole fillings of the first catalyzer, (six beds of take are example, by the first catalyst filling to three top beds, by the second catalyst filling three beds extremely on the lower), interlayer in present embodiment is loaded, and has better propene yield and catalyst life.
In another embodiment of the present invention, the filling mode of described the first catalyzer and the second catalyzer is: on each beds of described the second reactor, load successively from top to bottom the first catalyzer, packing layer and the second catalyzer, described packing layer can be the customary filler such as Ceramic Balls of inertia.
In the method for the invention, the preferred filling mode of described the first catalyzer and the second catalyzer is: on each beds of described the second reactor, load successively from top to bottom the first catalyzer, packing layer and the second catalyzer, described the first catalyzer and the amount of fill of the second catalyzer on each beds increase from top to bottom successively, such as increasing successively 5wt%～25wt%, preferred 10wt%～20wt%, better product stream is carried out to catalyzed reaction, further promote production of propylene reaction.
For n beds in described the second reactor, its from top to bottom can be called the first beds, the second beds ..., n-1 beds and most end beds (also referred to as n beds).Described the first product stream is introduced into described the second reactor as the charging of the second reactor; Described the second product stream obtains after separation comprises C
2, C
4, C
5and C
6the recycle hydrocarbons product stream of component is introduced into described the second reactor as the charging of the second reactor equally.
According to the preferred embodiment of the present invention, described the first product stream carries out gas-water separation, after separated water outlet, the vapor phase product stream of gained is delivered to respectively each beds of the second reactor after mixing with described recycle hydrocarbons product stream, separating obtained liquid product stream (be the aqueous solution, be wherein dissolved with a small amount of methyl alcohol and dme) deliver to respectively the second reactor second to most end beds.Drive vapor phase product stream and liquid product flow point into material, be more conducive to temperature of reactor and control, save temperature of charge regulation and control cost; Meanwhile, the vapor phase product stream after separated water outlet be more conducive to reaction carry out.
The further preferred embodiment according to the present invention, separating obtained vapor phase product stream mix with described recycle hydrocarbons product stream after feeding temperature on described the first beds be 450～490 ℃, inlet amount is that separating obtained vapor phase product stream is mixed the 15wt%～25wt% of total amount with described recycle hydrocarbons product stream; Separating obtained vapor phase product stream mix with described recycle hydrocarbons product stream after described second to the feeding temperature on most end beds be 220～250 ℃; Separating obtained liquid product material is 20～45 ℃ at the described second feeding temperature to most end beds.
The present invention is on the basis of further investigation MTP reaction mechanism, for existing MTP process characteristic, for improving propone output, by loading two kinds of catalyzer that acidity is different, make recycle hydrocarbons part catalytic pyrolysis on the stronger beds of acidity, generate small molecules hydro carbons and react with methanol/dimethyl ether participation MTP, effectively reduce carbon deposit and generate; Avoid the target product-olefin hydrocarbon molecules generating in preparing propylene from methanol reaction process that secondary reaction generation alkane and the macromole aromatic hydrocarbons such as hydrogen transference and aromizing occur in the stronger beds of acidity simultaneously, improve propene yield, the extending catalyst life-span.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of a kind of embodiment of the reaction unit that adopts in method of the present invention.Embodiment
Below in conjunction with accompanying drawing, the present invention is described in detail, but the present invention is not limited to this.
As shown in Figure 1, described reaction unit comprises the first reactor 1 (being DME reactor) and the second reactor 4 (being MTP reactor), in described the first reactor 1, be longitudinally provided with 2 beds, in described the second reactor 4, be provided with 6 beds 5, wherein, the methanol feeding of described the first reactor 1 is divided into two strands: after first strand of feeding preheating, from the top of described the first reactor 1, enter, carry out the strong exothermal reaction of methanol dehydration dimethyl ether synthesis; Second burst of charging for example, without preheating (described second strand of material keeps the temperature of 20 ℃～40 ℃), deliver between two beds in described the first reactor 1, mix with the reaction product of described first burst of charging, absorb strong exothermal reaction institute liberated heat, and proceed methyl alcohol dimethyl ether synthesizing reaction.
Described the first product stream is through separating tank 6 gas-liquid separations, and after separated water outlet, the vapor phase product stream of gained is mixed with described recycle hydrocarbons product stream by gas phase pipeline 2 and delivered to respectively on second reactor 4 each beds 5, on the first to the 6th beds; Separating obtained liquid product stream (be mainly water, and be dissolved on a small quantity methyl alcohol and dme in water) is delivered to respectively the second to the 6th beds of the second reactor 4 through liquid phase pipeline 3, to regulate each reaction bed temperature.
Below in conjunction with embodiment and comparative example, the present invention is further detailed.
In following examples and comparative example, described A catalyzer is the HZSM-5 molecular sieve catalyst of embodiment 2 preparations in CN201210531577.6;
Described B catalyzer is the Mo-HZSM-5 catalyzer of preparing in embodiment 2 in CN201110293745.8;
Described C catalyzer is the catalyzer of embodiment 4 preparations in CN201310172615.8.
Embodiment 1
In order to evaluate the reasonableness based on preparing propylene from methanol novel process, adopt the processing condition of mold trial device analoging industrial device as shown in Figure 1 to test, wherein the first reactor (being DME reactor) inner catalyst is γ-Al
2o
3(selecting the DME-1 type catalyzer of Clariant Co., Ltd), minute two-layer filling.The filling mode of described the second catalyst in reactor is: the catalyst A that is 1:1 by mass ratio and C load the first to the 6th beds to described the second reactor after evenly mixing.
Wherein, the methanol feeding amount of described the first reactor is 2.5kg/h, and the filling total amount of described the first catalyst reactor is 1.8kg, reaction pressure 0.8MPa.The filling total amount of described the second catalyst reactor is 2.5kg, reaction pressure 0.09MPa.
The methanol feedstock of 75wt% is preheating to after approximately 280 ℃, from the first reactor head, enters, without the residue methyl alcohol (temperature is about 35 ℃) of preheating, deliver to catalyst bed lamellar spacing.
After the material of delivering to the first beds of described the second reactor through gas phase pipeline is preheating to 470 ℃, enter the second reactor, all the other are cooled on 220～250 ℃ of second to the 6th beds of delivering to the second reactor.The temperature that enters the material of described the second reactor through liquid phase pipeline is about 30～40 ℃.Experimental result is in Table 1.
Embodiment 2
Be with the difference of embodiment 1, the filling mode of described the second catalyst in reactor is: the superiors of catalyst A from the beds of described the second reactor down interlayer load to corresponding beds, catalyzer C loads to remaining beds, and the mass ratio of catalyst A and C is 1:1.Experimental result is in Table 1.
Embodiment 3
Be with the difference of embodiment 1, the filling mode of described the second catalyst in reactor is: on each beds of described the second reactor, load successively from top to bottom catalyst A, packing layer and catalyzer C, the mass ratio of catalyst A and C is 1:1.Experimental result is in Table 1.
Embodiment 4
Be with the difference of embodiment 3, catalyzer C is replaced with to catalyst B.Experimental result is in Table 1.
Embodiment 5
Be with the difference of embodiment 3, the mass ratio of catalyst A and C is 2:1.Experimental result is in Table 1.
Embodiment 6
Be with the difference of embodiment 3, the filling quality of catalyst A and C the from first to the 6th beds progressively increases 0.1kg.Experimental result is in Table 1.
Comparative example 1
Be with the difference of embodiment 1, in described the second reactor, only load catalyst A.Experimental result is in Table 1.
Comparative example 2
Be with the difference of embodiment 1, in described the second reactor, only load catalyst B.Experimental result is in Table 1.
Comparative example 3
Be with the difference of embodiment 1, in described the second reactor, only load catalyzer C.Experimental result is in Table 1.
Table 1
Claims (7)
1. a method for preparing propylene from methanol, comprises and utilizes the first reactor and the second reactor to carry out preparing propylene from methanol reaction; Wherein, described the first reactor is for methyl alcohol dimethyl ether synthesizing reaction, to obtain the first product stream; Described the first product stream comprises dme, water and unreacted methyl alcohol;
Described the second reactor is for the propylene reaction processed of described the first product stream, to obtain the second product stream; And be longitudinally provided with a plurality of beds in described the second reactor, each beds of described the second reactor is filled with the first catalyzer and the second catalyzer, described the first catalyzer is HZSM-5 molecular sieve catalyst, and described the second catalyzer is the catalyzer of HZSM-5 molecular sieve catalyst gained after metal load or phosphorus modification;
Described the second product stream is isolated to and comprises C
2, C
4, C
5and C
6the recycle hydrocarbons product stream of component, sends into described recycle hydrocarbons product stream in described the second reactor again.
2. the method for claim 1, it is characterized in that, in described the second reactor, the filling mode of described the first catalyzer and the second catalyzer is: the mixture of described the first catalyzer mixing and the second catalyzer is loaded respectively to each beds to described the second reactor;
Or described the first catalyzer from the superiors of described beds down interlayer load the beds to described the second reactor, described the second catalyst filling is to described remaining beds of the second reactor;
Or on each beds of described the second reactor, load successively from top to bottom the first catalyzer, packing layer and the second catalyzer.
3. method as claimed in claim 2, it is characterized in that, in described the second reactor, the filling mode of described the first catalyzer and the second catalyzer is: on each beds of described the second reactor, load successively from top to bottom the first catalyzer, packing layer and the second catalyzer.
4. the method described in any one in claim 1-3, is characterized in that, the mass ratio of described the first catalyzer and the second catalyzer is 1:2～2:1, is provided with 4～8 beds in described the second reactor.
5. method as claimed in claim 4, is characterized in that, described the second catalyzer is the catalyzer of HZSM-5 molecular sieve catalyst gained after phosphorus modification.
6. the method for claim 1, is characterized in that, the mass ratio of described the first catalyzer and the second catalyzer is 1:1～2:1.
7. method as claimed in claim 3, is characterized in that, described the first catalyzer and the second catalyzer increase from the top down successively in the amount of fill of each beds of described the second reactor.
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| CN105523876A (en) * | 2015-12-17 | 2016-04-27 | 神华集团有限责任公司 | Method for preparing propylene from methanol |
| CN107721791A (en) * | 2017-10-26 | 2018-02-23 | 神华集团有限责任公司 | The preparation system and preparation method of a kind of preparing propylene from methanol |
| TWI618692B (en) * | 2015-11-17 | 2018-03-21 | 中國石油化工科技開發有限公司 | Method and reaction equipment for preparing dimethyl ether and olefin from methanol |
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| CN103086874A (en) * | 2013-01-09 | 2013-05-08 | 烟台万华聚氨酯股份有限公司 | Utilization method of tertiary butyl alcohol coproduced by using device for producing epoxypropane by using propene and iso-butane cooxidation method |
| CN103242125A (en) * | 2013-04-28 | 2013-08-14 | 西南化工研究设计院有限公司 | Method for synthesizing propylene by using methanol |
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| CN101624192A (en) * | 2009-08-10 | 2010-01-13 | 大唐国际化工技术研究院有限公司 | ZSM-5 type molecular sieve for catalyst for reaction for preparing propylene from methanol and/or dimethyl ether |
| CN103086874A (en) * | 2013-01-09 | 2013-05-08 | 烟台万华聚氨酯股份有限公司 | Utilization method of tertiary butyl alcohol coproduced by using device for producing epoxypropane by using propene and iso-butane cooxidation method |
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| TWI618692B (en) * | 2015-11-17 | 2018-03-21 | 中國石油化工科技開發有限公司 | Method and reaction equipment for preparing dimethyl ether and olefin from methanol |
| US10029966B2 (en) | 2015-11-17 | 2018-07-24 | China Petroleum & Chemical Corporation | Method and reaction equipment for preparing dimethyl ether and olefin from methanol |
| KR101902952B1 (en) * | 2015-11-17 | 2018-10-01 | 차이나 페트로리움 앤드 케미컬 코포레이션 | Method and reaction equipment for preparing dimethyl ether and olefin from methanol |
| CN105523876A (en) * | 2015-12-17 | 2016-04-27 | 神华集团有限责任公司 | Method for preparing propylene from methanol |
| CN107721791A (en) * | 2017-10-26 | 2018-02-23 | 神华集团有限责任公司 | The preparation system and preparation method of a kind of preparing propylene from methanol |
| CN107721791B (en) * | 2017-10-26 | 2023-09-22 | 神华集团有限责任公司 | Preparation system and preparation method for preparing propylene from methanol |
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