CN103333040B - Low energy consumption propylene production technology - Google Patents
Low energy consumption propylene production technology Download PDFInfo
- Publication number
- CN103333040B CN103333040B CN201310251451.8A CN201310251451A CN103333040B CN 103333040 B CN103333040 B CN 103333040B CN 201310251451 A CN201310251451 A CN 201310251451A CN 103333040 B CN103333040 B CN 103333040B
- Authority
- CN
- China
- Prior art keywords
- propylene
- production technology
- water
- product
- carrier gas
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 56
- 238000005516 engineering process Methods 0.000 title claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- 238000005265 energy consumption Methods 0.000 title claims abstract description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 126
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000003054 catalyst Substances 0.000 claims abstract description 32
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 27
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 27
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 23
- 238000006266 etherification reaction Methods 0.000 claims abstract description 23
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 9
- 150000001336 alkenes Chemical class 0.000 claims abstract description 8
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 48
- 239000012159 carrier gas Substances 0.000 claims description 41
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 26
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 22
- 239000002808 molecular sieve Substances 0.000 claims description 12
- 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 12
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- 230000018044 dehydration Effects 0.000 claims description 8
- 238000006297 dehydration reaction Methods 0.000 claims description 8
- 238000012546 transfer Methods 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 5
- 229960004217 benzyl alcohol Drugs 0.000 claims description 5
- 239000003915 liquefied petroleum gas Substances 0.000 claims description 5
- 239000000470 constituent Substances 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 238000009834 vaporization Methods 0.000 claims description 2
- 230000008016 vaporization Effects 0.000 claims description 2
- 239000002351 wastewater Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 7
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 3
- -1 propylene, ethylene Chemical group 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 2
- 239000003085 diluting agent Substances 0.000 abstract 3
- 239000005977 Ethylene Substances 0.000 abstract 1
- 239000008213 purified water Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 38
- 239000000203 mixture Substances 0.000 description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 239000007789 gas Substances 0.000 description 9
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 8
- 239000003245 coal Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000004587 chromatography analysis Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- VHOQXEIFYTTXJU-UHFFFAOYSA-N Isobutylene-isoprene copolymer Chemical group CC(C)=C.CC(=C)C=C VHOQXEIFYTTXJU-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000013536 elastomeric material Substances 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Substances OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 235000003642 hunger Nutrition 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- ULSIYEODSMZIPX-UHFFFAOYSA-N phenylethanolamine Chemical compound NCC(O)C1=CC=CC=C1 ULSIYEODSMZIPX-UHFFFAOYSA-N 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 230000037351 starvation Effects 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000007039 two-step reaction 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
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
-
- 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)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a low energy consumption propylene production technology, which comprises the following steps of (1) after mixing raw material methyl alcohol and diluent gas, carrying out etherification reaction, after mixing the primary product and the stream of the diluent gas with steam water and refined hydrocarbon and heat exchanging, preparing olefin so as to obtain a secondary product; (2) separating the secondary product so as to obtain propylene, ethylene, C1-C3 alkane, C4-C6 components comprising olefin and alkane, C7 and heavy components comprising arene; and (3) taking the vaporized purified water obtained through separation as part of the steam water and circulating to step (1), taking the products of ethylene, C1-C2 alkane, C4-C6 as the refined hydrocarbon, and returning to an OTP (one time programmable) reactor for preparing olefin continuously. According to the preparation method, the problem that high propylene yield needs a large amount of steam water and the problem of selectivity in the MTP (methanol to propylene) technology are solved, and the purposes of water saving and energy saving are finally realized through comprehensive regulation of diluent gas, refined hydrocarbon and catalyst carbon deposit quantity.
Description
Technical field
The present invention relates to the preparation method of propylene, be specifically related to a kind ofly use methyl alcohol or dme for raw material and the propylene production technology of object of saving water and energy can be reached.
Background technology
Propylene is a kind of important basic chemical industry raw material in modern chemical industry, and its demand constantly increases.The traditional production line of propylene is the steam cracking of petroleum naphtha and the catalytic cracking product as ethene coproduction.Along with the consumption of oil reserve, International Crude Oil rises steadily, cause being that the cost of raw material production propylene constantly raises with oil, and the ethane resource that the Middle East is cheap, make the path of ethane dehydrogenation to ethene compare petroleum naphtha route and more there is the market competitiveness, the production source of Secondary Shocks propylene, has finally caused with comparatively cheap Coal Chemical Industry Route---the research boom of preparing propylene from methanol (MTP) technology again.When current crude oil price very high and be also difficult to from now on decline, for the China of oil starvation, weak breath, rich coal, above Technology highlights stronger competitive power and far-reaching strategic importance more.
Known in the industry, need to pass into a large amount of steam water in MTP reaction, the thermal capacitance of water is utilized to carry out most of heat of absorption reaction releasing on the one hand, in addition on the one hand, under hot conditions, water can remove the partially acidic position of molecular sieve, improve the selectivity of product propylene, finally, water can also play reduction methanol partial pressure, improves the effect of propene yield.At present, the water resources ownership per capita in the main coal place of production of China and unit area water resources recoverable amount are only 1/10 of national level.The mean level (ML) of comprehensive industry, the water loss of producing one ton of coal liquifaction is at present about 9 tons, and olefin hydrocarbon making by coal is about 20 tons, and coal derived DME is about 12 tons, and coal preparing natural gas (methane) water loss is 6 tons, and coal-ethylene glycol is about 9 tons.In view of this, the high water consumption of Coal Chemical Industry becomes maximum secret worry and weakness.
High water consumption also results in high energy consumption.In MTP technique, water enters reactor with water vapor form, and after eventually passing disengaging zone, water has become the water of frozen state.If this part water is become gaseous state from liquid state after phase transformation, then the steam water of low temperature is heated to the high-temperature steam water of reactor inlet, this two-part energy consumption is also very high.So the technology of saving water and energy has become the trend of the times of MTO technology promotion development.
CN1431982A discloses a kind of method of preparing propylene from methanol, is Lurgi company fixed bed MTP technology popularization to one of the support technology of industrialized unit.In the method, methanol steam is first obtained by reacting the first the mixture steam containing dme under the effect of the first catalyzer, then this mixture steam generates the mix products containing propylene again under the effect of zeolite catalyst, and this two-step reaction is designated as DME reaction and OTP reaction respectively.This patent reports in the mixed gas be made up of DME reactor outlet and need to guarantee the water vapor containing q.s, account for 40 ~ 80% of mixed gas volume ratio.CN101023047B discloses and uses the technology that alcoholic oxygenate is propylene by moving bed technique and etherification step, and this technology is provided with an etherification reaction zone before oxygenatedchemicals propylene (OTP) reaction zone, but the catalyzer that employing two kinds is different.Thinner consumption in this patent OTP reactions steps is preferably about 0.5 ~ 5:1 for every mole of oxygenate equivalent, is conducive to generating the level of propylene to make the dividing potential drop of oxygenate drop to.CN1989086B discloses the technology using moving bed technique oxygenate to be converted into propylene, and the mol ratio of this patent requirements thinner and oxygenate is 0.1 ~ 5:1, and thinner used is water, methane, aromatic hydrocarbons.As can be seen here, no matter being fixed-bed process or moving bed process, is that propylene process all needs to rely on higher water vapor ratio by methanol conversion.
Summary of the invention
The invention provides a kind of propylene production technology of less energy-consumption, this propylene production technology mainly solves in MTP technique of the prior art to be needed to ensure a large amount of steam water, just can obtain high propylene yield and optionally problem.
A propylene production technology for less energy-consumption, comprises the following steps:
(1) be passed into after material benzenemethanol being mixed with carrier gas in DME reactor to contact with catalyst for etherification and carry out etherification reaction, obtain comprising methyl alcohol, dme, a product of water and the stream stock of carrier gas, then by after the same steam water of stream stock of a product obtaining and carrier gas, freshening hydrocarbon mixed heat transfer, enter into OTP reactor to contact with pre-carbon deposited catalyst and carry out olefine reaction processed, generate secondary product;
(2) secondary product that step (1) obtained sends into disengaging zone, carries out dewatering, after oxide removal, is separated and obtains propylene, ethene, C
1~ C
3alkane, C
4~ C
6containing component and the C of alkene and alkane
7and the above heavy constituent containing aromatic hydrocarbons;
(3) as some vapor water after the vaporization of purifying waste water disengaging zone dehydration in step (2) obtained, the ethene that disengaging zone is obtained, C
1~ C
2alkane, C
4~ C
6component in product except iso-butylene and divinyl, as freshening hydrocarbon, is back to OTP reactor and continues olefine reaction processed;
Described carrier gas is made up of at least one in freshening hydrocarbon component.
Water account for the very large proportion of incoming flow stock in MTP reaction, part water is changed into carrier gas in the present invention, be used for reducing methanol partial pressure, improve propene yield, utilize the freshening hydrocarbon component with larger thermal capacitance to replace the thermal capacitance of water contribution simultaneously, control the temperature rise of reactor, in addition, utilize coked catalyst adjustment of acidity, the effect that water regulates acidity of catalyst position can be reached, the selectivity of final raising propylene, reaches the object reducing feed water energy efficient.
In step (1), as preferably, described material benzenemethanol and carrier gas mol ratio 1:0.05 ~ 5.Described methanol feedstock, after overflash, heat exchange, enters DME reactor reaction with carrier gas, and generate the mixture of dme, methyl alcohol, water etc., the carrier gas composition of DME reactor outlet and content do not change.
As preferably, described carrier gas is methane or LPG(liquefied petroleum gas (LPG)).The molecular weight of above-mentioned carrier gas, the molecular weight of carrier gas is less, under unit mass feed conditions, just can provide more volume numbers, more favourable to reduction methanol partial pressure.In addition, these carrier gas are not easy to provide proton, in reaction process, Product olefins can not be transformed into saturated alkane.
In step (1), described etherification reaction condition is: feedstock inlet temperature 180 ~ 280 DEG C, and temperature out is 220 ~ 350 DEG C, and pressure is 0.1 ~ 2.1MPa, and methanol quality air speed is 1 ~ 25h
-1.It is a thermopositive reaction that methanol dehydration generates dme process, the heat that reaction produces is about 10KJ/mol methyl alcohol, therefore, in DME reactor, passes into carrier gas, the heat of reaction release not only can be utilized the temperature increase of carrier gas, reduce the temperature difference that carrier gas enters OTP reactor.In addition, the large thermal capacitance that carrier gas has, can control in rational scope by the temperature of etherification reaction, is unlikely to make DME reactor temperature runaway, causes generating OTP product ahead of time, reduces the yield of final propylene.
In step (1), as preferably, a described product and the mol ratio of steam water are 1:0.5 ~ 4, and described carrier gas and the mol ratio of steam water are 0.05 ~ 5:1, deduct the part of carrier gas in the stream stock that wherein product to refer to from DME reactor out.Now, after a described product and the stream stock of carrier gas and steam water and freshening hydrocarbon mixed heat transfer, wherein a part is introduced into OTP reactor and carries out OTP reaction with the catalyst exposure with pre-carbon deposit, generates the product being rich in propylene.
As preferably, in step (1), the condition of described olefine reaction processed is: feedstock inlet temperature 440 ~ 510 DEG C, and temperature out is 460 ~ 530 DEG C, and pressure is 0.1 ~ 1.1MPa, and methanol quality air speed is 0.3 ~ 12h
-1.
In step (1), described catalyst for etherification is aluminum oxide or acid molecular sieve catalyst, and described pre-carbon deposited catalyst is acid molecular sieve catalyst, preferably has the modified molecular screen of ZSM-5 pore passage structure or SAPO-34 pore passage structure.In OTP reactor, the carbon content of pre-carbon deposited catalyst is 1.5% ~ 20%, and after pre-carbon deposited catalyst comes from DME reactor reaction, carbon deposited catalyst or reclaimable catalyst still retain the catalyzer of certain carbon content after regeneration.Catalyst carbon deposit process first from the strong acidic site of molecular sieve, when carbon deposit to a certain extent time, the strong acidic site of molecular sieve is occupied by coke gradually, starts to attack weak acid position simultaneously.Propylene is formed in weak acid position, therefore, after catalyzer contains certain carbon deposit, not only can the duct of modulation molecular sieve, and reduce the generation of macromolecular substance, can also the acidity of modulation molecular sieve, improve the selectivity of propylene.
In step (2), the logistics of the secondary product of described OTP reactor outlet, after heat exchange, dehydration and oxide removal, obtains propylene, ethene, C respectively
1~ C
3alkane, C
4~ C
6containing component, the C of alkene and alkane
7and the above heavy constituent containing aromatic hydrocarbons.Propylene is as main purpose product-collecting, and aromatic hydrocarbons is collected as byproduct, C
4iso-butylene in component is as the material collection producing isoprene-isobutylene rubber, and a small amount of divinyl is also as producing elastomeric material collection, and propane and a small amount of butane are collected as liquefied gas.In order to improve the yield of propylene further, by methane, ethane, ethene and the C except iso-butylene, divinyl
4~ C
6the ratio that hydrocarbon is 0.1 ~ 10:1 according to the mol ratio of freshening hydrocarbon and a product stream is back to OTP reactor, or carries out ethene, butene inverse disproportionation propylene, or carries out C
4+ olefin cracking preparation of propylene reacts.The recycle of freshening hydrocarbon, not only increases the yield of propylene, also contribute to large thermal capacitance simultaneously, is beneficial to the control of temperature of reactor.
Described DME reactor types is fixed bed or moving-bed, and described OTP reactor is fixed bed or moving-bed or fluidized-bed.
Heat-exchanger rig is provided with outside described OTP reactor.Described heat-exchanger rig is positioned at outside fixed-bed reactor and/or multiple moving-burden bed reactor.Outside fixed bed/moving-burden bed reactor, heat-exchanger rig is set, not only can remove the reaction heat produced in reaction process, be convenient to the temperature of reaction that better control often walks reaction, and the heat be swapped out can the material of preheating each reaction zone entrance, save the input of utility heat, reach the object of utilization system heat energy.When thermal discharge is excessive, the chilling device now set up outside fixed bed/moving-burden bed reactor can effectively remove unnecessary reaction heat, the Quench liquid in chilling device from etherification reaction product, i.e. the mixture of dme, methyl alcohol, water etc.
Compared with the existing technology, the present invention has the following advantages:
(1) the present invention passes into carrier gas in etherification reaction, not only control the temperature of DME reactor, prevent OTP product from generating too early, affect propylene ultimate yield, also the reaction heat that etherification reaction discharges is used for heating carrier gas, improve the temperature out of carrier gas, reduce the entrance temperature difference that carrier gas enters OTP reactor;
(2) the present invention's utilize carrier gas instead of effect that part water is reduced methanol partial pressure, utilize the large thermal capacitance of freshening hydrocarbon to make up the thermal capacitance reduced because reducing steam water simultaneously, reach the object controlling reactor temperature rise, finally utilize the coke content modulation acidic zeolite of OTP catalyzer, ensure that the highly selective of propylene.
Accompanying drawing explanation
Fig. 1 is the schema of the propylene production technology of less energy-consumption of the present invention;
In figure, solid line represents main flow, and dotted line represents intermediate feed flow process, and m represents material benzenemethanol, and x represents carrier gas, and w represents steam water, and r represents freshening hydrocarbon, and for the purpose of simplifying the description, the parts such as well heater, pipeline, valve omit in the drawings.
Embodiment
As shown in Figure 1, adopt a moving-bed with etherification reaction zone, OTP reaction zone adopts three moving-burden bed reactors to be example, is specifically described.
Be sent to the moving-burden bed reactor M0 of DME reaction zone by feed pot from the regenerated catalyst of breeding blanket, moved down by gravity, rely on action of gravity respectively through moving-bed M1, OTP reaction zone, OTP reaction zone moving-bed M2, OTP reaction zone moving-bed M3 from M0 catalyzer out, controlling discharge velocity allows the residence time of the catalyzer of firm charging in OTP reaction zone be 50-300 hour, sent for regeneration after drawing catalyzer from last reactor outlet of OTP reaction zone, catalyzer after regeneration returns to feed pot, by moving-bed circulating reaction.
Material benzenemethanol m is mixed and heated to etherification reaction zone M0 after heat exchange temperature in carrier gas x forms a incoming flow stock, a flows stock and catalyst exposure, reaction generates the mixture than the methyl alcohol of temperature in comparatively high temps, dme and water, and wherein the composition of reactor outlet carrier gas does not change with amount.M0 reactor outlet stream stock is three strands, wherein one and steam water w, formed after b incoming flow stock is heated to OTP reaction zone first paragraph moving-burden bed reactor M1 temperature in after freshening hydrocarbon r mixed heat transfer, with pre-carbon deposited catalyst contact reacts, outlets products forms c and flows stock and pass into second segment moving-burden bed reactor M2 after heat exchange mixes with the Mischung of carrier gas with another strand of etherification reaction product, outlets products flows with residue one etherification reaction product and the mixture f of carrier gas after stock mixes through heat exchange again and passes into the 3rd section of moving-burden bed reactor M3 for d, outlets products r is through heat exchange, dehydration, be separated after oxide removal, the methane separated, ethane, ethene and except iso-butylene, after C4 ~ C6 hydrocarbon r beyond divinyl and the heat exchange of etherification reaction product, return to OTP reaction zone and continue reaction.
Embodiment 1
The catalyzer that the present embodiment adopts is the spherical or bar shaped catalyst of the ZSM-5 molecular sieve of particle 1.0-3.0mm, the raw material adopted is methyl alcohol, carrier gas is the mixture of methane, ethane, and mol ratio is between the two 2:8, and the mol ratio of carrier gas and methyl alcohol is 3:1.
Etherification reaction zone adopts fixed-bed reactor, and temperature in is 180 DEG C, temperature out 220 DEG C, and pressure is normal pressure, methanol quality air speed 25h
-1.The mol ratio of freshening hydrocarbon and a product is 0.5:1, and the mol ratio of steam water and a product is 4:1.
OTP reaction zone adopts fixed-bed reactor, and temperature in is 440 DEG C, normal pressing operation, methanol quality air speed 12h
-1.Material in reactor reacts with the catalyst exposure with 15% pre-carbon deposit, outlets products stream stock temperature is at 480 DEG C, through heat exchange, dehydration with oxide removal after, further separation obtains principal product propylene and by product aromatic hydrocarbons and iso-butylene and divinyl etc., methane, ethane, ethene and the C4 ~ C6 hydrocarbon except iso-butylene, divinyl is back to OTP reaction zone and continues reaction.Gas product adopts gas chromatographic analysis, and the carbon base absorption rate of propylene is 60%.
Other operations are with above-mentioned embodiment.
Embodiment 2
The catalyzer that the present embodiment adopts is the ZSM-5 molecular sieve spherical catalyst of particle 1.0-2.5mm, and the raw material adopted is methyl alcohol, and carrier gas is methane, and the mol ratio of carrier gas and methyl alcohol is 3:1.
Etherification reaction zone adopts a moving-burden bed reactor, and temperature in is 230 DEG C, temperature out 260 DEG C, pressure 1.8MPa, methanol quality air speed 10h
-1.Methyltertiarvbutyl ether reactor outlets products is divided into two gangs of A and B, mass ratio is 1:1, freshening hydrocarbon and steam water all mix with first gang of methyltertiarvbutyl ether reactor outlets products A, wherein freshening hydrocarbon is 2.0:1 with the mol ratio of the mixture of methyl alcohol, dme, water in stream stock A, and steam water is 2:1 with the mol ratio of the mixture of methyl alcohol, dme, water in stream stock A.
OTP reaction zone adopts two moving-burden bed reactors, and first moving-burden bed reactor temperature in is 470 DEG C, operates, methanol quality air speed 4h under 0.6MPa pressure
-1; Second moving-burden bed reactor temperature in is 460 DEG C, normal pressing operation, methanol quality air speed 4/h; Stream stock A enters the catalyst exposure with 10% pre-carbon deposit that first moving-burden bed reactor and methyltertiarvbutyl ether reactor shift out and reacts, outlets products stream stock temperature is at 480 DEG C, after stream stock B mixed heat transfer, enter into second moving-burden bed reactor together to react, the residence time of catalyzer in OTP reaction zone is 100 hours.Product stream stock temperature is drawn at 480 DEG C from reactor outlet; After dehydration and oxide removal, be separated further and obtain principal product propylene and by product aromatic hydrocarbons and iso-butylene and divinyl etc., methane, ethane, ethene and the C4 ~ C6 hydrocarbon except iso-butylene, divinyl except are back to OTP reaction zone and continue to react.Gas product adopts gas chromatographic analysis, and the carbon base absorption rate of propylene is 70%.
Other operations are with above-mentioned embodiment.
Embodiment 3
The catalyzer that the present embodiment adopts is the ZSM-5 molecular sieve spherical catalyst of particle 1.0-2.5mm, and the raw material adopted is methyl alcohol, and carrier gas is methane, butane, and the mol ratio of three is followed successively by 6:1, and the mol ratio of carrier gas and methyl alcohol is 5:1.
Etherification reaction zone adopts a moving-burden bed reactor, and temperature in is 260 DEG C, temperature out 300 DEG C, pressure 2.1MPa, methanol quality air speed 5h
-1.Methyltertiarvbutyl ether reactor outlets products is divided into three gangs of A, B, C, mass ratio is 2:3:5, freshening hydrocarbon and steam water all mix with first gang of methyltertiarvbutyl ether reactor outlets products A, wherein freshening hydrocarbon is 10:1 with the mol ratio of the mixture of methyl alcohol, dme, water in stream stock A, and steam water is 1:1 with the mol ratio of the mixture of methyl alcohol, dme, water in stream stock A.
OTP reaction zone adopts three moving-burden bed reactors, and first moving-burden bed reactor temperature in is 480 DEG C, operates, methanol quality air speed 2h under 0.8MPa pressure
-1; Second moving-burden bed reactor temperature in is 470 DEG C, operates, methanol quality air speed 2/h under 0.5MPa pressure; 3rd moving-burden bed reactor temperature in is 460 DEG C, operates, methanol quality air speed 2/h under 0.2MPa pressure; Stream stock A enters the catalyst exposure with 1.5% pre-carbon deposit that first moving-burden bed reactor and methyltertiarvbutyl ether reactor shift out and reacts, outlets products stream stock temperature is at 485 DEG C, after stream stock B mixed heat transfer, enter into second moving-burden bed reactor together to react, outlets products stream stock temperature is at 485 DEG C, after stream stock C mixed heat transfer, enter into the 3rd moving-burden bed reactor together and react, the residence time of catalyzer in OTP reaction zone is 250 hours.Product stream stock temperature is drawn at 485 DEG C from reactor outlet; After dehydration and oxide removal, be separated further and obtain principal product propylene and by product aromatic hydrocarbons and iso-butylene and divinyl etc., methane, ethane, ethene and the C4 ~ C6 hydrocarbon except iso-butylene, divinyl except are back to OTP reaction zone and continue to react.Gas product adopts gas chromatographic analysis, and the carbon base absorption rate of propylene is 69%.
Other operations are with above-mentioned embodiment.
Find out from above-mentioned three embodiments, according to processing method disclosed by the invention, while reducing steam water consumption, higher Propylene Selectivity can also be obtained.
Claims (9)
1. a propylene production technology for less energy-consumption, is characterized in that, comprises the following steps:
(1) be passed into after material benzenemethanol being mixed with carrier gas in DME reactor to contact with catalyst for etherification and carry out etherification reaction, obtain comprising methyl alcohol, dme, a product of water and the stream stock of carrier gas, then by after the same steam water of stream stock of a product obtaining and carrier gas, freshening hydrocarbon mixed heat transfer, enter into OTP reactor to contact with pre-carbon deposited catalyst and carry out olefine reaction processed, generate secondary product;
(2) secondary product that step (1) obtained sends into disengaging zone, carries out dewatering, after oxide removal, is separated and obtains propylene, ethene, C
1~ C
3alkane, C
4~ C
6containing component and the C of alkene and alkane
7and the above heavy constituent containing aromatic hydrocarbons;
(3) as some vapor water after the vaporization of purifying waste water disengaging zone dehydration in step (2) obtained, the ethene that disengaging zone is obtained, C
1~ C
2alkane, C
4~ C
6component in product except iso-butylene and divinyl, as freshening hydrocarbon, is back to OTP reactor and continues olefine reaction processed;
Described carrier gas is methane or liquefied petroleum gas (LPG).
2. the propylene production technology of less energy-consumption according to claim 1, is characterized in that, in step (1), and described material benzenemethanol and mol ratio 1:0.05 ~ 5 of carrier gas.
3. the propylene production technology of less energy-consumption according to claim 1, is characterized in that, in step (1), the condition of described etherification reaction is: feedstock inlet temperature 180 ~ 280 DEG C, temperature out is 220 ~ 350 DEG C, and pressure is 0.1 ~ 2.1MPa, and methanol quality air speed is 1 ~ 25h
-1.
4. the propylene production technology of less energy-consumption according to claim 1, is characterized in that, in step (1), a described product and the mol ratio of steam water are 1:0.5 ~ 4, and described carrier gas and the mol ratio of steam water are 0.05 ~ 5:1.
5. the propylene production technology of less energy-consumption according to claim 1, is characterized in that, in step (1), described freshening hydrocarbon and the mol ratio of a product stream are 0.1 ~ 10:1.
6. the propylene production technology of less energy-consumption according to claim 1, it is characterized in that, in step (1), the condition of described olefine reaction processed is: feedstock inlet temperature 440 ~ 510 DEG C, temperature out is 460 ~ 530 DEG C, pressure is 0.1 ~ 1.1MPa, and methanol quality air speed is 0.3 ~ 12h
-1.
7. the propylene production technology of less energy-consumption according to claim 1, is characterized in that, in step (1), described catalyst for etherification is aluminum oxide or acid molecular sieve catalyst, and described pre-carbon deposited catalyst is acid molecular sieve catalyst.
8. the propylene production technology of less energy-consumption according to claim 7, is characterized in that, the carbon content of described pre-carbon deposited catalyst is 1.5% ~ 20%.
9. the propylene production technology of less energy-consumption according to claim 1, is characterized in that, described DME reactor types is moving-bed or fixed bed, and described OTP reactor types is moving-bed, fluidized-bed or fixed bed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310251451.8A CN103333040B (en) | 2013-06-21 | 2013-06-21 | Low energy consumption propylene production technology |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310251451.8A CN103333040B (en) | 2013-06-21 | 2013-06-21 | Low energy consumption propylene production technology |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103333040A CN103333040A (en) | 2013-10-02 |
| CN103333040B true CN103333040B (en) | 2015-04-01 |
Family
ID=49241268
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310251451.8A Expired - Fee Related CN103333040B (en) | 2013-06-21 | 2013-06-21 | Low energy consumption propylene production technology |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103333040B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103694077B (en) * | 2013-12-03 | 2015-09-30 | 浙江大学 | A kind of propylene that produces can the reaction process of coproduction high octane gasoline component |
| CN104784953B (en) * | 2015-03-26 | 2016-09-21 | 神华集团有限责任公司 | A kind of product piece-rate system for preparing propylene from methanol and chilling system thereof |
| CN106748610B (en) * | 2016-12-30 | 2024-02-09 | 神华集团有限责任公司 | System and method for preparing propylene tail oil by using methanol in value-added mode |
| CN109020772A (en) * | 2017-06-12 | 2018-12-18 | 神华集团有限责任公司 | The method and system of methanol-to-olefins |
| CN113912569B (en) * | 2020-07-10 | 2024-04-26 | 中国石油化工股份有限公司 | Propylene direct epoxidation method capable of reducing diluent gas dosage |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102344328B (en) * | 2011-07-25 | 2014-03-12 | 浙江大学 | Semi-continuous method for converting methyl alcohol into propylene by using moving bed technology |
| CN102924214B (en) * | 2012-10-30 | 2015-02-25 | 浙江大学 | Production technique of propylene |
| CN102942435B (en) * | 2012-11-06 | 2014-12-17 | 浙江大学 | Reaction technology using moving bed technique to convert methanol into propylene |
-
2013
- 2013-06-21 CN CN201310251451.8A patent/CN103333040B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN103333040A (en) | 2013-10-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103242123B (en) | A kind of separation method of low carbon olefin gas | |
| CN101830769B (en) | Method for converting methanol into propylene | |
| CN205235935U (en) | A equipment for following oxygen compound produces alkene | |
| CN103333040B (en) | Low energy consumption propylene production technology | |
| CN102942435B (en) | Reaction technology using moving bed technique to convert methanol into propylene | |
| CN103980082B (en) | A kind of method of preparing propylene from methanol | |
| CN101293801B (en) | Method for preparing dimethyl ether, low carbon olefin hydrocarbon with combination of methanol dehydration catalytic pyrolysis | |
| CN104557361A (en) | Multifunctional system and method for preparing ethylene, propylene and aromatic hydrocarbons by converting methanol and/or dimethyl ether | |
| CN104177214B (en) | A kind of catalytic cracking rich gas and methanol to olefins reaction product composite liberation method | |
| CN202081036U (en) | Mixed gas separating system in MTP reaction | |
| CN101928598B (en) | Method and system for producing gasoline and propylene by integrating heavy oil catalytic cracking with oxygen-containing compound conversion | |
| CN102351629B (en) | Method for producing propylene and high-octane gasoline from methanol | |
| CN101891576A (en) | Process and device for preparing low-carbon olefin by methanol and/or dimethyl ether | |
| CN104355960B (en) | A kind of method by preparing propylene from methanol and BTX | |
| CN106831288B (en) | The MTP method of mixed alcohol side entry feed | |
| CN104557415A (en) | System and method for preparing aromatic hydrocarbon and coproducing liquefied gas by converting methanol and/or dimethyl ether | |
| CN105130730A (en) | Technological method for preparing light hydrocarbons through methanol by means of continuous regeneration moving beds and production system | |
| CN105130729A (en) | Durene-poly-generation technological method and production system for preparing light hydrocarbon through methyl alcohol | |
| CN102924214B (en) | Production technique of propylene | |
| CN102344328B (en) | Semi-continuous method for converting methyl alcohol into propylene by using moving bed technology | |
| CN103980083B (en) | A kind of method of preparing propylene from methanol | |
| CN101234946B (en) | Method for separating low-carbon olefin mixed gas | |
| CN103694077B (en) | A kind of propylene that produces can the reaction process of coproduction high octane gasoline component | |
| CN102060644B (en) | Method for preparing olefin by dehydration of methanol | |
| CN105523876B (en) | A kind of method by preparing propylene from methanol |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150401 Termination date: 20160621 |