CN101629090A - Technique for producing hydrocarbon products rich in propylene by methanol - Google Patents
Technique for producing hydrocarbon products rich in propylene by methanol Download PDFInfo
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- CN101629090A CN101629090A CN200910075175A CN200910075175A CN101629090A CN 101629090 A CN101629090 A CN 101629090A CN 200910075175 A CN200910075175 A CN 200910075175A CN 200910075175 A CN200910075175 A CN 200910075175A CN 101629090 A CN101629090 A CN 101629090A
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Abstract
The invention relates to a technique for producing hydrocarbon products rich in propylene by methanol, comprising: after heat exchange is carried out between mixture of the methanol and water vapor and products generated in the reaction of preparing hydrocarbon by using the methanol, the reaction is firstly carried out through a dimethyl ether reactor filled with dimethyl ether catalyst, so that at least part of the methanol is converted into dimethyl ether; the mixture of the methanol, water and the dimethyl ether at an outlet of the dimethyl ether reactor is heated by a heater and then has reaction in a reactor which is used for preparing hydrocarbon by using the methanol and filled with molecular sieve based catalyst, so that the methanol and the dimethyl ether are transformed into hydrocarbon mixture rich in the propylene; after passing through a heat exchanger and a cooler, products generated at an outlet of the reactor for preparing hydrocarbon by using the methanol enter a gas-liquid separator, the gas part of the hydrocarbon mixture which is below C4 and rich in the propylene is obtained by separation, the separated liquid enters an oil-water separator, and C5<+> mixed hydrocarbon and the water can be respectively obtained, and part of the water can be recycled. The technique has the advantages of reducing the manufacturing cost, greatly improving the filling efficiency of catalyst and the effective utilization rate of the volume of the reactors, and simplifying the operation method.
Description
Technical field
The invention belongs to a kind of technology, relate in particular to a kind of technology that is rich in the hydrocarbon products of propylene by methanol production by the methanol production hydrocarbon products.
Background technology
Technology by the methanol production hydrocarbon products has a large amount of records in existing document.Wherein, also delivered a large amount of patents as the technology and the catalyzer of ethene and propylene about by the methanol production low molecular weight olefins.
The technology of the preparing propylene from methanol of document record, what major part adopted is two-stage process, wherein first section is adopted catalyzer such as aluminum oxide, with at least a portion methanol conversion is dme, second section employing has the molecular sieve catalyst of five-membered ring structure, to contain the methyl alcohol of part dme and water at least, be converted into the hydrocarbon mixture product of low molecular weight olefins such as being rich in ethene, propylene.
Send out in the technology for above-mentioned two sections, at first near small part methanol conversion is a dme in first section reactor, and one of its purpose is that partial reaction heat obtains to discharge in the conversion of the first step, thereby reduces the thermal load of second section reaction.
Technology about methanol conversion system low molecular weight olefins is described, can be referring to U.S. Pat 4058576, US4025575, US4471150 etc., and German patent DE A3604636, DEC3228269, European patent EP 91104102.8, and world patent WO2007/140844 etc.
Yet still there are some difficulties that are difficult to overcome in the technology of methanol conversion system low molecular weight olefins.Wherein main difficulty is to keep higher low molecular weight olefins selectivity, again reaction heat is rationally shifted out reactor.In order to solve this class problem, the process using of existing patent record several different methods.
German patent DE 10027159A1 has announced a kind of technology of methanol production propylene.The technology that this patent is described has comprised two-stage reaction.The process using that this patent is announced tubular reactor, second-stage reaction heat is shifted out by the indirect heat exchange mode at conversion zone.But obviously there is the catalyst loading and unloading difficulty in tubular reactor, many, problem such as the reactor volume effective rate of utilization is low consuming time.
U.S. Pat 4025575 has been announced a kind of technology of methyl alcohol system low molecular weight olefins, and this patent adopts the method that adds thinner to reduce the reaction process thermal insulation warming.Its concrete method is, in first section reactor, is dme with at least a portion methanol conversion at first, again with methyl alcohol/dme mixture, together with a kind of thinner, as nitrogen, methane or water vapour together, enter the second stage reactor that molecular sieve catalyst is housed.Because the existence of thinner, the thermal insulation warming of second stage reactor can be controlled effectively.But this technology is when adopting nitrogen to be thinner, and the defective of existence is that nitrogen is very difficult with separating of product, greatly reduces the feasibility of technology.And the technology that provides according to this patent adopts water to have a strong impact on the yield of low molecular weight olefins again as thinner, has particularly reduced the yield of propylene.
EP91104102.8 has announced a kind of low molecular weight olefins production technique, and this patent wishes to solve the problem that US4025575 adopts water to reduce as propene yield under the thinner condition.Regrettably, in the technology that this patent is announced, water and the normal weight ratio of methyl alcohol as thinner only can reach 0.1～1.5, still can not effectively solve the problem that two sections conversion reaction heat shift out, therefore, the technology that this patent is announced still adopts tubular reactor, thereby also has tubular reactor inherent defective.
WO2007/140844 has announced a kind of reactor of methanol-to-olefins, in the hope of addressing the above problem.The reactor that this patent is announced adopts a kind of in an airtight vertical vessel, by a plurality of reaction order are installed, between reaction order, by fog system, with the mode that heat-eliminating medium and partial reaction material spray into, reaches the purpose of control reaction temperature.Though the reactor that this patent provides has been avoided the part defective of tubular reactor,, the setting of a plurality of reaction order has caused the defective of inside reactor complex structure, operational difficulty.Simultaneously, also there is the low problem of volume effective rate of utilization in this reactor.
Summary of the invention
The objective of the invention is for a kind of working method simply, reactor volume effective rate of utilization height can effectively be controlled reaction heat, and what the low molecular weight olefins selectivity was higher is rich in the technology of the hydrocarbon products of propylene by methanol production.
The technology that methyl alcohol system provided by the present invention is rich in the hydrocarbon mixture of propylene is methyl alcohol and water vapor mixture at first to be carried out dme (DME) transform, make to the small part methanol conversion be dme.The mixture of methyl alcohol, water and dme makes methyl alcohol and dme all be converted into the hydrocarbon mixture that is rich in propylene through methanol conversion system hydrocarbon (MTHC) reaction.Methanol conversion system hydrocarbon (MTHC) reactor adopts adiabatic reactor, realizes control to thermal insulation warming by add a certain amount of water in material benzenemethanol.
Concrete processing step of the present invention is as follows:
(1) methyl alcohol and water vapor mixture at first react by dme (DME) reactor that dimethyl ether catalyst is housed by after generating the material heat exchange with methyl alcohol system hydrocarbon (MTHC), make to the small part methanol conversion be dme;
(2) after the methyl alcohol of dme (DME) reactor outlet, water and dme mixture heater via heat up, react by methyl alcohol system hydrocarbon (MTHC) reactor that molecular sieve catalyst is housed, making methyl alcohol and dimethyl ether conversion is the hydrocarbon mixture that is rich in propylene;
(3) enter gas-liquid separator behind methyl alcohol system hydrocarbon (MTHC) reactor outlet resultant process interchanger, the water cooler, separate the C that obtains being rich in propylene
4The gas part of following hydrocarbon mixture is separated the liquid that obtains and is entered water-and-oil separator, obtains C respectively
5 +Hydrocarbon mixture and water, a part of water cycle is used.
Aforesaid alcohol system hydrocarbon (MTHC) reactor adopts adiabatic reactor.
Aforesaid dimethyl ether catalyst is γ-Al
2O
3Or the γ-Al of modification
2O
3Catalyzer.Dimethyl ether reactor inlet material temperature is 200～380 ℃, and the temperature of outlet material is 250～450 ℃; The weight space velocity of dimethyl ether catalyst is 0.2～2.0h
-1, be preferably 0.5～1.2h
-1The mixture of first alcohol and water is 0.6～17h with respect to the gross weight air speed of dimethyl ether catalyst
-1, be preferably 1.75～13h
-1Working pressure is in 0.1～3.0MPa scope, and preferred working pressure is 0.1～1.0MPa.
The aforesaid weight ratio that enters between dme (DME) reactor water and the methyl alcohol is 2.0～7.5, preferably 2.5～6.5.
Aforesaid molecular sieve catalyst is the molecular sieve catalyst with five-membered ring structure, particularly the H-ZSM-5 molecular sieve catalyst of H-ZSM-5 molecular sieve catalyst or process modification.Methanol conversion system hydrocarbon (MTHC) reactor inlet material temperature scope is 300～480 ℃, is preferably 350～450 ℃, and the outlet material temperature range is preferably 400～550 ℃.The difference of temperature out and inlet temperature can not preferably be not more than 100 ℃ greater than 150 ℃.The conversion of the methyl alcohol of the methanol conversion system of entering hydrocarbon (MTHC) reactor and dme is for after the methyl alcohol weight, is 0.2～2.0h with respect to the weight space velocity of methanol conversion system hydrocarbon (MTHC) catalyzer
-1, be preferably 0.5～1.2h
-1The mixture of methyl alcohol, dme and water is 0.6～17h with respect to the gross weight air speed of methanol conversion system hydrocarbon (MTHC) catalyzer
-1, be preferably 1.75～13h
-1Working pressure can be the content of propylene in the middle of the raising hydrocarbon mixture in 0.1～3.0MPa scope, technology provided by the invention is preferably under the lower pressure carries out, and preferred working pressure is 0.1～1.0MPa.
Aforesaid methanol conversion system hydrocarbon (MTHC) reactor is provided with minimum 2, preferably is provided with 3～5.Can realize the serialization of production process by the switching regeneration of methanol conversion system hydrocarbon (MTHC) reactor.
Description of drawings
Fig. 1 is a schema of the present invention
As shown in the figure, 1 methyl alcohol storage tank, 2 dimethyl ether (DME) reactor, the 3rd, heater, the 4th, methanol conversion hydrocarbon processed (MTHC) reactor, the 5th, heat exchanger, the 6th, cooler, the 7th, gas-liquid separator, the 8th, oil water separator, the 9th, the water in the water tank, 10,11,12,13,14,15,16,17,18,19,20,21,22,23,24,25th, pipeline.
Technique provided by the invention can be further specified in conjunction with process flow diagram shown in Figure 1. As shown in the figure, be stored in methyl alcohol and the water that is stored in the water tank 8 in the methyl alcohol storage tank 1, respectively after pipeline 10 and 11 mixes, enter in the heat exchanger 5, after methanol conversion hydrocarbon processed (MTHC) reactor 4 outlet material heat exchange intensification, enter in dimethyl ether (DME) reactor 2 through pipeline 12,13, at least part of methyl alcohol is converted into dimethyl ether here. Dimethyl ether (DME) reactor 2 outlet materials enter in the heater 3 through pipeline 14,15, after material is heated to reaction temperature, through pipeline 16,17, enter methanol conversion hydrocarbon processed (MTHC) reactor 4. In reactor 4, methyl alcohol and dimethyl ether are converted into the hydro carbons mix products and the water that are rich in propylene under the effect of methanol conversion hydrocarbon processed (MTHC) catalyst. Methanol conversion hydrocarbon processed (MTHC) reactor 4 outlet materials enter heat exchanger 5 through pipeline 18, and carry out heat exchange from the methyl alcohol in the methyl alcohol storage tank 1 and from the water in the water tank 9, and cooling enters cooler 6 through pipeline 19 again, further cooling. Material after the cooling enters gas-liquid separator 7 through pipeline 20 and carries out separating of gaseous product and product liquid, and gas partly is mainly the following hydrocarbon mixture of the C4 that is rich in propylene, leaves system through pipeline 21. The liquid of telling from gas-liquid separator 7 mainly is C5 +Hydrocarbon mixture and water, these materials enter oil water separator 8 through pipeline 22 and carry out water-oil separating, and oil phase is C5 +Hydrocarbon mixture is transported to outside the system through pipeline 23, and from the water that oil water separator 8 is told, a part effluxes through pipeline 24, and another part is got back to water tank 9 through pipeline 25.
In the above-mentioned technique provided by the invention, in dimethyl ether (DME) reactor 2, filling be any can be the catalyst of dimethyl ether with at least part of methanol conversion, such as γ-Al2O
3, and the γ-Al of modification2O
3Catalyst. When the mixture of first alcohol and water passes through this reactor, have at least the part methanol dehydration to generate dimethyl ether.
According to the performance of selected dimethyl ether catalyst, can control the heat exchange state of heat exchanger 5, with the temperature of the mixture of adjusting the first alcohol and water in suitable scope. According to the difference of the dimethyl ether catalyst that adopts, the temperature of pipeline 12 interior materials is adjusted in 200～380 ℃ of scopes, with satisfy the dimethyl ether reactor inner catalyst to temperature needs.
Methanol conversion is that the reaction of dimethyl ether is exothermic reaction, and temperature of charge is further enhanced. Dimethyl ether reactor 2 adopts adiabatic reactor, has catalyst loading and unloading conveniently, the advantage that the reactor volume utilization ratio is high. Simultaneously, adopt adiabatic reactor that the temperature of material is suitably improved, thereby effectively utilize reaction heat, reduce the energy consumption of overall process. It is 250～450 ℃ from the temperature of dimethyl ether (DME) reactor 2 material out.
Enter the heater 3 through pipeline 15 from dimethyl ether (DME) reactor 2 material out, as required, further heating, the temperature of raising material is to reach the temperature requirement of methanol conversion hydrocarbon processed (MTHC) reactor 4.
Methanol conversion hydrocarbon processed (MTHC) reactor 4 is fixed bed adiabatic reactor, filling alcohol transforms hydrocarbon processed (MTHC) catalyst in the reactor, these catalyst first-selections have the molecular sieve catalyst of five-membered ring structure, particularly the H-ZSM-5 molecular sieve catalyst of H-ZSM-5 molecular sieve catalyst or process modification.
According to the performance of the selected catalyst of methanol conversion hydrocarbon processed (MTHC) reactor 4, can by adjusting the state of heater 3, reach the purpose of adjusting temperature of charge in the pipeline 16,17. The temperature of material namely is the temperature of methanol conversion hydrocarbon processed (MTHC) reactor 4 entrance materials in the pipeline 16,17.
According to technique provided by the invention, the temperature range of methanol conversion hydrocarbon processed (MTHC) reactor inlet material is 300～480 ℃. According to the performance of selected catalyst, the temperature range of methanol conversion hydrocarbon processed (MTHC) reactor inlet material is preferably 350～450 ℃.
Methanol conversion is that the reaction (MTHC) of hydrocarbon is strong exothermal reaction. Under adiabatci condition, the temperature of reaction mass is carried out and can be raise gradually with reaction. Because the performance of damaging catalyst falls in too high temperature, therefore, need the temperature of control material in the acceptable scope of catalyst.
Technique provided by the invention is to realize controlling the purpose of methanol conversion hydrocarbon processed (MTHC) reactor 4 interior material adiabatic temperature rises by add water in material benzenemethanol.
Get purpose for reaching control methanol conversion hydrocarbon processed (MTHC) reactor 4 interior material adiabatic temperature rises, can recently realize from the water of water tank 9 and from the weight between the methyl alcohol in the methyl alcohol storage tank 1 by control. Increase from the water of water tank 9 and from the weight ratio between the methyl alcohol in the methyl alcohol storage tank 1, then methanol conversion hydrocarbon processed (MTHC) reactor 4 interior material adiabatic temperature rises reduce, on the contrary, reduce from the water of water tank 9 and from the weight ratio between the methyl alcohol in the methyl alcohol storage tank 1, then methanol conversion hydrocarbon processed (MTHC) reactor 4 interior material adiabatic temperature rises increase.
According to technology provided by the invention, do not suffer damage for guaranteeing the catalyzer that fills in methanol conversion system hydrocarbon (MTHC) reactor 4, the difference of this reactor outlet temperature and inlet temperature can not preferably be not more than 100 ℃ greater than 150 ℃.
According to technology provided by the invention, methanol conversion system hydrocarbon (MTHC) reactor 4 outlet material temperature ranges are preferably 400～550 ℃.
According to method provided by the invention, be 2.0～7.5 from the water of water tank 9 and from the weight ratio between the methyl alcohol in the methyl alcohol storage tank 1, preferably 2.5～6.5.
According to technology provided by the invention, material benzenemethanol is 0.2～2.0h with respect to the weight space velocity of dimethyl ether catalyst
-1, be preferably 0.5～1.2h
-1The mixture of first alcohol and water is 0.6～17h with respect to the gross weight air speed of dimethyl ether catalyst
-1, be preferably 1.75～13h
-1
In the technology provided by the invention, many methanol conversion system hydrocarbon (MTHC) reactor can be set.Like this, when the situation of catalyst carbon deposition inactivation occurring, can realize the serialization of production process by the switching regeneration of methanol conversion system hydrocarbon (MTHC) reactor.As shown in the figure, the technology that methyl alcohol system provided by the invention is rich in the hydrocarbon mixture of propylene is provided with minimum 2 methanol conversion system hydrocarbon (MTHC) reactor, preferably is provided with 3～5.
Above-mentioned technology provided by the invention, working pressure can carry out under 0.1～3.0MPa, is the content of propylene in the middle of the raising hydrocarbon mixture, and technology provided by the invention is preferably under the lower pressure carries out, and preferred working pressure is 0.1～1.0MPa.
According to technology provided by the invention, methanol conversion system hydrocarbon (MTHC) reactor 4 outlet materials are in interchanger 5, with from the methyl alcohol in the methyl alcohol storage tank 1 and from the mixture heat exchange of the water in the water tank 9, after reducing temperature, after the water cooler cooling, enter gas-liquid separator 7 and carry out gas-liquid separation again.Separating the gas part that obtains, is the following hydrocarbon mixture of C4 that is rich in propylene, is the main products of technology provided by the invention.This mixture leaves system by pipeline 21, can further separate as required or process.
Gas-liquid separator 7 separates the liquid portion that obtains, and mainly is C
5 +The mixture of hydrocarbon product and water enters water-and-oil separator 8 through piping 22 and further separates, and the oil phase part that obtains mainly is C
5 +Hydrocarbon product is through pipeline 23 output systems.A water part is returned water tank 9, and remainder is through pipeline 24 output systems.
Advantage of the present invention is as follows:
1, dme (DME) reactor and methyl alcohol system hydrocarbon (MTHC) reactor have all adopted adiabatic reactor, and any heat exchange and cold shock device are not set in reactor, make structure of reactor simplify, manufacturing cost reduces, and catalyst loading efficient and reactor volume effective rate of utilization increase substantially.
2, the control of methyl alcohol system hydrocarbon (MTHC) reactor thermal insulation warming realizes by adding entry in the material benzenemethanol again, has avoided the circulation of hydrocarbons, has simplified working method.
3, enter dimethyl ether reactor after methyl alcohol and water mixture and the heat exchange of methyl alcohol system hydrocarbon (MTHC) reactor outlet material and react, make the dimethyl ether reactor easy control of temperature, the utilising efficiency of reaction heat improves simultaneously.
Embodiment
Technology of the present invention can further specify by following examples.But methanol conversion system provided by the invention is rich in the technology of the hydrocarbon mixture of propylene and is not limited to embodiment.
Technical process and working method are as follows.Be stored in methyl alcohol and the water that is stored in the water tank 8 in the methyl alcohol storage tank 1, respectively after pipeline 10 and 11 mixes, enter in the interchanger 5, after methyl alcohol system hydrocarbon (MTHC) reactor 4 outlet material heat exchange intensification, enter in dme (DME) reactor 2 through pipeline 12,13, be converted into dme here to small part methyl alcohol.Dme (DME) reactor 2 outlet materials enter in the well heater 3 through pipeline 14,15, after material is heated to temperature of reaction, through pipeline 16,17, enter methanol conversion system hydrocarbon (MTHC) reactor 4.In reactor 4, methyl alcohol and dme are converted into the hydro carbons mix products and the water that are rich in propylene under the effect of molecular sieve catalyst.Methanol conversion system hydrocarbon (MTHC) reactor 4 outlet materials enter interchanger 5 through pipeline 18, and carry out heat exchange from the methyl alcohol in the methyl alcohol storage tank 1 and from the water in the water tank 8, and cooling enters water cooler 6 through pipeline 19 again, further cooling.Material after the cooling enters gas-liquid separator 7 through pipeline 20 and carries out separating of gaseous product and product liquid, and gas partly is mainly the following hydrocarbon mixture of C4 that is rich in propylene, leaves system through pipeline 21.The liquid of telling from gas-liquid separator 7 mainly is C
5 +Hydrocarbon mixture and water, these materials enter water-and-oil separator 8 through pipeline 22 and carry out oily water separation, and oil phase is C
5 +Hydrocarbon mixture is transported to outside the system through pipeline 23, and from the water that water-and-oil separator 8 is told, a part effluxes through pipeline 24, and another part is got back to water tank 9 through pipeline 25.
Table 1.1 is processing parameters of present embodiment, and table 1.2 is physical parameters of the employed catalyzer of present embodiment, and table 1.3 is reaction results of present embodiment.
Table 1.1 embodiment 1 main technologic parameters
Table 1.2 embodiment 1 catalyzer physical parameter
| Physical parameter | Specific surface area m 2/g | Mean pore size nm | Pore volume ml/g | B acid μ g/g | L acid μ g/g | The Si/Al ratio |
| ??γ-Al 2O 3 | ??213 | ??6.9 | ??0.56 | ??- | ??- | ??- |
| The H-ZSM-5 molecular sieve | ??382 | ??0.48 | ??0.1033 | ??0.105 | ??0.483 | ??218 |
Table 1.3 embodiment 1 reaction result
| Methyl alcohol/dimethyl ether conversion rate % | ??100％ |
| Primary product C atom selectivity % | |
| Ethene | ??5.6 |
| Propylene | ??50.7 |
| Butylene | ??21.1 |
| The C5+ hydrocarbon | ??20.1 |
| Other | ??2.5 |
| Add up to | ??100 |
Embodiment 2-5
Adopt the catalyzer identical with embodiment 1, the weight ratio of change water and methyl alcohol, other parameter constants, the reaction result that obtains sees Table 2.
Table 2 embodiment 2-5 parameter and reaction result
| |
|
|
|
|
| Water and methyl alcohol weight ratio | ??2.5 | ??4 | ??6 | ??7.5 |
| The DME reactor inlet temperature (℃) | ??200 | ??200 | ??300 | ??300 |
| DME reactor outlet temperature (℃) | ??350 | ??320 | ??400 | ??380 |
| The MTHC reactor inlet temperature (℃) | ??350 | ??350 | ??420 | ??400 |
| MTHC reactor outlet temperature (℃) | ??550 | ??470 | ??500 | ??450 |
| Methanol conversion (%) | ??100 | ??100 | ??100 | ??100 |
| Primary product C atom selectivity (%) | ||||
| Ethene | ??5.3 | ??4.7 | ??5.2 | ??6.5 |
| Propylene | ??52.2 | ??46.4 | ??48.7 | ??50.0 |
| Butylene | ??21.4 | ??23.6 | ??22.1 | ??25.3 |
| The C5+ hydrocarbon | ??10.0 | ??21.0 | ??20.1 | ??14.6 |
| Other | ??11.1 | ??4.3 | ??3.9 | ??3.6 |
| Add up to | ??100 | ??100 | ??100 | ??100 |
Embodiment 6-9
The all conditions of embodiment 6-9 is identical with embodiment 1, only changes working pressure.Table 3 is results of embodiment 6-9.
From embodiment 6-9 as can be seen, along with the raising of working pressure, the selectivity of propylene obviously descends, and the selectivity of C5+ hydrocarbon raises gradually.
Table 3 embodiment 6-9 reaction result
| |
|
|
|
|
| Working pressure (MPa) | ??0.2 | ??0.5 | ??1.0 | ??2.0 |
| Methanol conversion (%) | ??100 | ??100 | ??100 | ??100 |
| Primary product C atom selectivity (%) | ||||
| Ethene | ??5.3 | ??4.7 | ??3.2 | ??1.5 |
| Propylene | ??43.2 | ??38.4 | ??31.3 | ??25.0 |
| Butylene | ??18.4 | ??16.6 | ??15.8 | ??12.3 |
| ?C 5 +Hydrocarbon | ??20.1 | ??28.5 | ??35.2 | ??50.8 |
| Other | ??13.0 | ??11.8 | ??14.5 | ??10.4 |
| Add up to | ??100 | ??100 | ??100 | ??100 |
Embodiment 10-13
The all conditions of embodiment 10-13 is identical with embodiment 1, only changes the weight space velocity of methyl alcohol, and the weight ratio of water and methyl alcohol.Table 4 is reaction results of embodiment 10-13
Table 4 embodiment 10-13 reaction result
| | | | | |
| Methyl alcohol weight space velocity (h -1) | ??0.2 | ??0.8 | ??1.2 | ??2 |
| The weight ratio of water and methyl alcohol | ??4 | ??5 | ??5 | ??6 |
| Methyl alcohol/dme/water gross weight air speed (h -1) | ??1.0 | ??4.8 | ??7.2 | ??14 |
| Methanol conversion (%) | ??100 | ??100 | ??100 | ??100 |
| Primary product C atom selectivity (%) | ||||
| Ethene | ??11.6 | ??10.8 | ??5.2 | ??1.5 |
| Propylene | ??52.8 | ??51.6 | ??48.7 | ??45.0 |
| Butylene | ??28.4 | ??25.0 | ??24.1 | ??20.3 |
| ??C 5 +Hydrocarbon | ??0 | ??8.6 | ??17.4 | ??22.8 |
| Other | ??7.2 | ??4.0 | ??4.6 | ??10.4 |
| Add up to | ??100 | ??100 | ??100 | ??100 |
Claims (17)
1. one kind is rich in the technology of the hydrocarbon products of propylene by methanol production, it is characterized in that comprising the steps:
(1) methyl alcohol and water vapor mixture at first react by the dimethyl ether reactor that dimethyl ether catalyst is housed by after generating the material heat exchange with methyl alcohol system hydrocarbon, make to the small part methanol conversion be dme;
(2) after methyl alcohol, water and the dme mixture heater via of dimethyl ether reactor outlet heat up, react by the methyl alcohol system hydrocarbon reactor that molecular sieve catalyst is housed, making methyl alcohol and dimethyl ether conversion is the hydrocarbon mixture that is rich in propylene;
(3) enter gas-liquid separator behind methyl alcohol system hydrocarbon reactor outlet resultant process interchanger, the water cooler, separate the C that obtains being rich in propylene
4The gas part of following hydrocarbon mixture is separated the liquid that obtains and is entered water-and-oil separator, obtains C respectively
5 +Hydrocarbon mixture and water, a part of water cycle is used.
2, as claimed in claim 1ly a kind ofly be rich in the technology of the hydrocarbon products of propylene, it is characterized in that described methyl alcohol system hydrocarbon reactor adopts adiabatic reactor by methanol production.
3, as claimed in claim 1ly a kind ofly be rich in the technology of the hydrocarbon products of propylene, it is characterized in that described dimethyl ether catalyst is γ-Al by methanol production
2O
3Or the γ-Al of modification
2O
3Catalyzer.
4, as claimed in claim 1ly a kind ofly be rich in the technology of the hydrocarbon products of propylene by methanol production, it is characterized in that described dimethyl ether reactor inlet material temperature is 200～380 ℃, the temperature of outlet material is 250～450 ℃; The weight space velocity of dimethyl ether catalyst is 0.2～2.0h
-1, the mixture of first alcohol and water is 0.6～17h with respect to the gross weight air speed of dimethyl ether catalyst
-1, the weight ratio that enters between dimethyl ether reactor water and the methyl alcohol is 2.0～7.5, working pressure is in 0.1～3.0MPa scope.
5, as claimed in claim 4ly a kind ofly be rich in the technology of the hydrocarbon products of propylene by methanol production, the weight space velocity that it is characterized in that described dimethyl ether catalyst is 0.5～1.2h
-1
6, as claimed in claim 4ly a kind ofly be rich in the technology of the hydrocarbon products of propylene by methanol production, the mixture that it is characterized in that described first alcohol and water is 1.75～13h with respect to the gross weight air speed of dimethyl ether catalyst
-1
7, as claimed in claim 4ly a kind ofly be rich in the technology of the hydrocarbon products of propylene, it is characterized in that the described weight ratio that enters between dimethyl ether reactor water and the methyl alcohol is 2.5～6.5 by methanol production.
8, as claimed in claim 4ly a kind ofly be rich in the technology of the hydrocarbon products of propylene, it is characterized in that described working pressure is 0.1～1.0MPa by methanol production.
9, as claimed in claim 1ly a kind ofly be rich in the technology of the hydrocarbon products of propylene, it is characterized in that described molecular sieve catalyst is a H-ZSM-5 molecular sieve catalyst or through the H-ZSM-5 molecular sieve catalyst of modification by methanol production.
10, as claimed in claim 1ly a kind ofly be rich in the technology of the hydrocarbon products of propylene by methanol production, it is characterized in that described methanol conversion system hydrocarbon reactor inlet material temperature scope is 300～480 ℃, the outlet material temperature range is 400～550 ℃.The difference of temperature out and inlet temperature can not be greater than 150 ℃, enter the methyl alcohol of methanol conversion system hydrocarbon reactor and dme conversion for after the methyl alcohol weight, are 0.2～2.0h with respect to the weight space velocity of methanol conversion system hydrocarbon catalyst
-1, the mixture of methyl alcohol, dme and water is 0.6～17h with respect to the gross weight air speed of methanol conversion system hydrocarbon catalyst
-1, reaction pressure is in 0.1～3.0MPa scope.
11, as claimed in claim 10ly a kind ofly be rich in the technology of the hydrocarbon products of propylene, it is characterized in that 350～450 ℃ of described methanol conversion system hydrocarbon reactor inlet material temperature scopes by methanol production.
12, as claimed in claim 10ly a kind ofly be rich in the technology of the hydrocarbon products of propylene, it is characterized in that the difference of described temperature out and inlet temperature is not more than 100 ℃ by methanol production.
13, a kind of technology that is rich in the hydrocarbon products of propylene by methanol production as claimed in claim 10, it is characterized in that described methyl alcohol that enters methanol conversion system hydrocarbon reactor and dme conversion for after the methyl alcohol weight, is 0.5～1.2h with respect to the weight space velocity of methanol conversion system hydrocarbon catalyst
-1
14, as claimed in claim 10ly a kind ofly be rich in the technology of the hydrocarbon products of propylene by methanol production, the mixture that it is characterized in that described methyl alcohol, dme and water is 1.75～13h with respect to the gross weight air speed of methanol conversion system hydrocarbon catalyst
-1
15, as claimed in claim 10ly a kind ofly be rich in the technology of the hydrocarbon products of propylene, it is characterized in that described working pressure is 0.1～1.0MPa by methanol production.
16, as claimed in claim 1ly a kind ofly be rich in the technology of the hydrocarbon products of propylene, it is characterized in that described methanol conversion system hydrocarbon reactor is provided with minimum 2 by methanol production.
17, as claimed in claim 15ly a kind ofly be rich in the technology of the hydrocarbon products of propylene, it is characterized in that described methanol conversion system hydrocarbon reactor is provided with 3～5 by methanol production.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103964990A (en) * | 2014-03-14 | 2014-08-06 | 惠生工程（中国）有限公司 | MTO (methanol toolefin) and steam crackingto olefin mixed separation technology |
| CN106220462A (en) * | 2016-07-31 | 2016-12-14 | 山西沸石科技有限公司 | A kind of fixed bed adiabatic reactor two-step method methanol converts the method producing hydrocarbon mixture |
| CN106146236B (en) * | 2015-05-15 | 2019-06-18 | 内蒙古丰汇化工有限公司 | The method that hydrocarbon products is prepared by methanol two-step method |
| CN110183301A (en) * | 2019-05-31 | 2019-08-30 | 国家能源投资集团有限责任公司 | Preparing propylene from methanol system and the method that feeds intake of driving is carried out using it |
| CN111218298A (en) * | 2020-01-14 | 2020-06-02 | 河北玺尧新能源科技有限公司 | Preparation method for producing aromatic hydrocarbon and olefin by using mixed alcohol |
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2009
- 2009-08-14 CN CN200910075175A patent/CN101629090A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103964990A (en) * | 2014-03-14 | 2014-08-06 | 惠生工程（中国）有限公司 | MTO (methanol toolefin) and steam crackingto olefin mixed separation technology |
| CN106146236B (en) * | 2015-05-15 | 2019-06-18 | 内蒙古丰汇化工有限公司 | The method that hydrocarbon products is prepared by methanol two-step method |
| CN106220462A (en) * | 2016-07-31 | 2016-12-14 | 山西沸石科技有限公司 | A kind of fixed bed adiabatic reactor two-step method methanol converts the method producing hydrocarbon mixture |
| CN106220462B (en) * | 2016-07-31 | 2019-01-25 | 山西沸石科技有限公司 | A kind of method that hydrocarbon mixture is produced in the conversion of fixed bed adiabatic reactor two-step method methanol |
| CN110183301A (en) * | 2019-05-31 | 2019-08-30 | 国家能源投资集团有限责任公司 | Preparing propylene from methanol system and the method that feeds intake of driving is carried out using it |
| CN110183301B (en) * | 2019-05-31 | 2022-06-28 | 国家能源投资集团有限责任公司 | Methanol-to-propylene system and method for starting and feeding by using same |
| CN111218298A (en) * | 2020-01-14 | 2020-06-02 | 河北玺尧新能源科技有限公司 | Preparation method for producing aromatic hydrocarbon and olefin by using mixed alcohol |
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