CN101928598B - Method and system for producing gasoline and propylene by integrating heavy oil catalytic cracking with oxygen-containing compound conversion - Google Patents
Method and system for producing gasoline and propylene by integrating heavy oil catalytic cracking with oxygen-containing compound conversion Download PDFInfo
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Abstract
The invention discloses a method and a system for producing gasoline and propylene by integrating heavy oil catalytic cracking with oxygen-containing compound conversion. The oil-gas separation part of the conventional heavy oil catalytic cracking device is integrated with a fixed bed reactor group for oxygen-containing compound catalytic conversion. The propylene and the gasoline are prepared from part of rich gas components in an oil-gas separator on the top of a catalytic cracking fractionating tower in an oil refinery and dry gas, light olefin components and organic oxygen-containing compounds from other crude oil secondary processing devices serving as raw materials under the action of a special catalyst, so that raw materials for catalytic cracking processing are expanded, the propylene yield of a catalytic cracking process is improved and the yield and quality of the gasoline can be improved. The invention provides a method and a device for increasing the yield of catalytic cracking gasoline and the propylene. The yield of catalytic cracking light olefin and the ratio of olefin products can be flexibly adjusted by only integrating the heavy oil catalytic cracking device with an oxygen-containing compound device; and the method and the system have the advantages of simple process, mature technology, small investment and easy implementation.
Description
Technical field
The present invention relates to a kind of integrating heavy oil catalytic cracking with oxygen-containing compound and transform method and the device of producing gasoline and propylene, more particularly, it is the fixed-bed reactor group at the partly integrated oxygenatedchemicals catalyzed conversion of product separation of the crude oil secondary processing devices such as existing heavy oil catalytically cracking equipment, the raw material of expansion catalytic cracking, improve productivity of propylene and quality of gasoline, productive rate, method and the device of the ratio of flexible catalytic cracking light olefin productive rate and olefin product kind.
Background technology
Along with the fast development of China's economy and the raising of people's living standard, demand for plastics such as high grade clean gasoline and polyolefine also rapidly increases, and the main raw material treated gasoline of this two series products and propylene are mainly from the heavy oil catalytic cracking process in the refining of petroleum.Since two thousand five, world's crude production rate descends continuously from peak value, and oil price continues run at high level, and the methyl alcohol overall throughput of the energy is supplied with the lasting demand that surpasses in continuous growth as an alternative.The crude oil in China shortage of resources, dependence on foreign countries for oil is high, and energy security is on the hazard; The throughput of China's methyl alcohol has broken through 3,000 ten thousand tons at present, the methanol-to-olefins project is still located in the demonstration, low ratio methanol gasoline national standard (M15) is also in formulation, cause alcohol ether industry working rate very low, the whole working rate of methyl alcohol industry is less than 50%, the average working rate of dme device has been down to about 20%, enterprise's production run difficulty.This has just formed a kind of strange phenomenon, same raw material as producing gasoline and propylene, and oil supply is not enough on the one hand, and methyl alcohol is seriously superfluous on the other hand.
Technology with the methanol production hydro carbons is divided three classes by the purpose product, preparing gasoline by methanol (MTG), preparing propylene from methanol (MTP) and Methanol light olefin (MTO).MTG technique was succeeded in developing by Mobil company in 1976, adopted the ZSM-5 molecular sieve catalyzer, and producing octane value is the high-grade gasoline of 90-95, and is very low without sulphur, benzene content in the gasoline.Reactor types is divided into two kinds of fixed bed and fluidized-beds, and the selectivity of gained gasoline in hydrocarbon products reaches respectively 80% and 60%.Lurqi company and Mobil company have developed the MTG technique of multitubular reactor form, yield of gasoline 35.7% cooperatively.(Coal Chemical Industry, 1994, (2): 13-20)
Germany Lurgi company has developed MTP technique, adopt the ZSM-5 molecular sieve catalyzer, operational path is to be that the MTP reactor that enters 3 parallel connections behind the dme (DME) reacts by methanol conversion, and dme and MTP all adopt fixed-bed reactor, wherein the MTP reactor be two open one standby.During normal running, single reactor methanol transformation efficiency reaches more than 90%, and through the cyclical operation of product alkene, Propylene Selectivity improves.(petrochemical technology and economy, 2008,24(4): 34)
The MTO technology is at first proposed by Mobil company.Nineteen ninety-five UOP/Hydro has developed jointly successfully MTO technique, adopts aperture SAPO-34 silicoaluminophosphamolecular molecular sieve catalyst, integrated with system cracking technique (OCP) of Total company after, the ethene of new MTO technique and the carbon back selectivity of propylene can reach more than 90%.The DMTO technique that the Dalian Chemistry and Physics Institute of the Chinese Academy of Sciences and Luoyang Petrochemical engineering corporation develop jointly also adopts aperture SAPO-34 silicoaluminophosphamolecular molecular sieve catalyst, and the carbon back selectivity of the ethene of catalyzer of new generation and propylene can reach more than 90%.The FMTP technique of Tsing-Hua University exploitation adopts aperture CHA/AEI intergrowth phase silicoaluminophosphamolecular molecular sieve catalyst, carries out Industrial demonstration in Huaihe River group in 2008, year processes 30,000 tons of methyl alcohol, can produce 10,000 tons of propylene.(chemical industry, 2009,27(1-2): 18-22)
Related developments take ZSM-5 molecular sieve as catalyzer from preparing light olefin by carbinol and gasoline is as follows:
CN100471825C discloses a kind of technique of preparing hydrocarbons produce from methanol by one-step method, material benzenemethanol is heated to temperature of reaction, enter in the methanol conversion that acid Si-Al zeolite molecular sieve catalyst is housed, at 300-500 ℃, 0.1-5.0MPa, the liquid air speed of methyl alcohol is under the 0.1-10.0h-1 condition, be converted into the hydrocarbon products mixture, refrigerated separation gets liquid C5+ hydrocarbon products and gas phase part, gas phase partly enters recycle compressor, a liquid part that obtains after the compression is left system as liquefied petroleum gas product, and another part mixes with material benzenemethanol as recycle stock, further reacts in the Returning reactor.It is short that the present invention has technical process, simple to operate, the advantage of reduced investment.
CN100438979C discloses a kind of preparation method of hydrocarbon molecular sieve catalyst by methanol transformation, and silicon source, template, aluminium source, mineral acid and deionized water are made colloid, gets directed agents after the reaction; With silicon source and directed agents, aluminium source, mineral acid and ionized water, add solubility lanthanum salts solution and make colloid, reaction, filtration, oven dry, roasting, the LaZSM-5 molecular sieve; The LaHZSM-5 molecular sieve is processed to get in the exchange of LaZSM-5 molecular sieve, and again with the binding agent kneading and compacting, oven dry, roasting get catalyzer.This catalyzer is higher for the gasoline fraction selectivity of the reaction of preparing gasoline by methanol hydro carbons, and oil product olefin(e) centent＜10%.
CN101182276A discloses a kind of method of preparing hydrocarbon products by methanol conversion, increase the total beds length of reactor, sidewall at reactor increases some to material import and export simultaneously, these material import and exports are divided into the beds in the reactor some sections shorter beds, the switching over of the valve by importing and exporting upper installation, make reaction mass by reactor the time, experience all the time shorter beds, when realizing that methyl alcohol transforms fully, reduce bed pressure drop, reach extending catalyst regeneration period and replacement cycle, simplify technological operation, enhance productivity and the purpose of process technology economic performance.
It is the method that contains C2 ~ C4 olefin product with methyl alcohol or dimethyl ether conversion that CN1352627A discloses a kind of, the method will contain the material of methyl alcohol or dme and contain 10 membered ring channel zeolites, such as ZSM-5, the contacted step of catalyzer, contact reacts is to be that the per pass conversion of 30-150PSia and methyl alcohol carries out less than 95% time at 370-480 ℃, methyl alcohol dividing potential drop.
CN1039392C discloses and has a kind ofly produced the ZSM-5 type zeolite catalyst of phosphorous, the rare earth element of light olefin process and pore structure conditioning agent and adopt dehydration reactor and the regenerate reaction process of multistage insulation fixed bed cracking reactor of blocked operation of 2 ~ n reaction one for methyl alcohol or dme, at high temperature (〉 400 ℃) once-through operation, be day to process on the device of methyl alcohol 0.7-1 ton in scale, methanol conversion 100%, C2 ~ C4 olefine selective can be greater than 85%, online runtime can be greater than 600 hours, and the single-pass operation cycle can be greater than 24 hours.
US7015369B2(MG) disclose from the method for methyl alcohol preparing propone, methyl alcohol is at first dewatered in a reactor generates dme, and reaction mixture enters at least two series connection fixed-bed reactor reactions again and generates propylene.
Although it is ripe that Methanol hydrocarbon technology is tending towards, the technology of the integrated processing methyl alcohol of heavy oil fluid catalytic cracking still is in the laboratory study stage.
CN 86101079A discloses a kind of catalyst cracking method, with methyl alcohol as reactant with oils gas oil for example, contact with fine grain ZSM-5 an acidic catalyst preferably, so that the catalytic cracking reaction of the reaction of methanol conversion of heat release and heat absorption heat balance haply.
Microporous and Mesoporous Materials, 1999, (29): 145 –, 157 reports have obtained thermally equilibrated reaction process with the Dehydration of methanol of heat release and the different hydrocarbons cracking reaction coupling of heat absorption.Utilize modified ZSM-5 zeolite to be catalyzer, 600-680 ℃ of reaction, reduced the productive rate of methane and COx in the independent Dehydration of methanol, hydrogen when obtaining higher yield of light olefin.
Journal of Chemical Industry and Engineering, 2006,57(4): 785-790 has reported the reaction process of methyl alcohol as the charging of catalytic cracking part, in the charging of 40% (massfraction) methanol aqueous solution, not under the condition of 550 ~ 600 ℃ of carbon deposited catalysts, temperature of reaction, the hydrocarbon productive rate of methanol conversion can reach 26.3% ~ 28.1% (massfraction), and low-carbon alkene accounts for 67.8% ~ 66.5% (massfraction) that hydrocarbon forms.
Petrochemical complex, 2009,38(3): 267-272 has reported the research of methyl alcohol and the mixing upgrading of fluid catalytic cracking gasoline on the small riser reactor, and methyl alcohol and FCC gasoline are mixing when improving quality of gasoline, is conducive to increase production reacted gas and improves liquid yield.
CN101104571A and CN101104576A disclose a kind of method of producing ethylene from ethanol by combination hydrocarbons catalytic conversion, original operation is kept in catalytic cracking, catalytic cracking regenerated catalyst flows out and is divided into two portions, wherein a part still contacts with hydrocarbon raw material, contact with ethanol raw material after another part cooling, ethanol contacts with the catalyzer that contains Y type zeolite, and the reaction product separator of flowing through obtains carbon deposited catalyst and purpose product ethene, and carbon deposited catalyst enters revivifier and carries out coke burning regeneration.The method ethanol conversion is up to more than 99 %, and the content of ethene is up to more than the 95 body % in the reformed gas product.
US2006/0229481A1 discloses in hydro carbons heat or catalytic cracking process and to have added CxH2x+1OCyH2y+1(x and y is 1-30) ethers, ethers is at least part of alkene that is cracked in reaction, and reduce the hydrocarbon cracking green coke.
Organic oxygen-containing compound and petroleum hydrocarbon that CN1206319C discloses a kind of coupling are raw material, adopt fluidized-bed reactor, be 25-100 containing the Si/Al weight ratio, carry out the method for catalytic cracking to prepare lower carbon olefin under the solid acid catalyst of the molecular sieve of 0.4-0.7nm and the effect of high-temperature vapor.Reaction conditions is: temperature 500-720 ℃, and the weight ratio 5-40:1 of catalyzer and petroleum hydrocarbon, the weight ratio 0.01-2:1 of organic oxygen-containing compound and petroleum hydrocarbon, the weight ratio 0-1:1 of water vapour and petroleum hydrocarbon.
CN101210190A discloses the method for a kind of heavy petroleum hydrocarbon and the common charging preparing low-carbon olefins of methyl alcohol and gasoline.The method utilizes methyl alcohol to replace the part heavy feed stock at fluidized catalytic cracker, on the composite molecular sieve catalyst that contains shape-selective molecular sieve that mass ratio is 1:0.1-1.0 and large pore molecular sieve, jointly refine out the premium product, simultaneously increased low carbon olefine output.Methyl alcohol accounts for the 1.5-50%(massfraction of stock oil), water injection rate accounts for the 5-50% of stock oil, and operational condition is temperature 480-600 ℃, pressure 0.01-0.51MPa, weight hourly space velocity 1.01-20.lh-1, agent-oil ratio 1.0-20.1.
From prior art as seen, methyl alcohol or other oxygenatedchemicals and petroleum hydrocarbon are subject to the catalyst activity and selectivity restriction with advancing catalyst cracker, and methanol conversion and olefine selective are all not high enough.Because the general amount of finish of China's methyl alcohol product installation is little, the place of production disperses, newly-built methyl alcohol process for producing hydrocarbons can not form scale and benefit.And China's catalytic cracking unit tricks is many, working ability is large, follow-up process matched therewith is complete, therefore utilizes existing catalyzed cracking processing ability to process the methyl alcohol of producing nearby, has not only solved the outlet of methyl alcohol, light oil and olefin yields can also be increased, the economic benefit of refinery can be obviously improved.Therefore, the crude oil secondary processing device such as development of new catalytic cracking and the integrated complete processing of methyl alcohol are very meaningful.
Summary of the invention
Main purpose of the present invention is to provide a kind of integrating heavy oil catalytic cracking with oxygen-containing compound to transform the method and system of producing gasoline and propylene, fixed-bed reactor group at partly integrated oxygenatedchemicals catalyzed conversions of crude oil secondary processing device product separation such as existing heavy oil fluid catalytic cracking, make the raw material expansion of catalyzed cracking processing, the productivity of propylene of catalytic cracking process can be improved, yield of gasoline and quality can be improved simultaneously.
Another object of the present invention is to provide a kind of oxygenatedchemicals to transform special-purpose catalyst and preparation method thereof, and this catalyzer has high Propylene Selectivity and low green coke when transforming methyl alcohol and light olefin, can farthest obtain the valuable product yield.
Technical scheme of the present invention
A kind of integrating heavy oil catalytic cracking with oxygen-containing compound transforms the system that produces gasoline and propylene, comprises catalytic cracking unit, characterized by further comprising the oxygenatedchemicals processing unit (plant);
Wherein said catalytic cracking unit comprises separation column and gas-liquid separator;
Described oxygenatedchemicals processing unit (plant) comprises a row fixed-bed reactor group, gas-liquid separator and heat-exchange system; The fixed-bed reactor outlet enters the gas-liquid separator of oxygenatedchemicals processing unit (plant) behind heat-exchange system;
The gas tube at the gas-liquid separator top at the separation column top of described catalytic cracking unit is drawn side line to the feeding part of a row fixed-bed reactor group of oxygenatedchemicals processing unit (plant), to realize the integrated of two covering devices;
Oxygenatedchemicals after vaporization enters a fixed-bed reactor group of equipping special-purpose catalyst and carries out conversion reaction, simultaneously draw the feeding part that side line enters into a row fixed-bed reactor group of oxygenatedchemicals processing unit (plant) from the part rich gas component of the gas-liquid separator of the fractionation cat head of catalytic cracking unit through above-mentioned, with the dry gas from other production equipments, the segmentation of light olefin component enter above-mentioned fixed-bed reactor group contact with above-mentioned special-purpose catalyst carry out conversion reaction and finish after, fixed-bed reactor outlet oil gas enters the gas-liquid separator of oxygenatedchemicals processing unit (plant) after the heat-exchange system cooling, the rich gas that the gas-liquid separator of oxygenatedchemicals processing unit (plant) ejects mixes the absorbing-stabilizing system of catalytic cracking unit with former catalytic cracking supercharging rich gas after supercharging, the gas-liquid separator stage casing is extracted raw gasline out and is mixed the absorbing-stabilizing system of catalytic cracking unit with former catalytic cracking raw gasline, discharges the additional circulating water system that enters of water at the bottom of the gas-liquid separator.
Described fixed-bed reactor group is that 2-5 fixed-bed reactor are connected in series or in parallel, can realize that at least one reactor carries out oxygenate conversion reaction, and other reactor carries out regenerative operation, so that integrated complete processing is moved continuously.
Filling special-purpose catalyst in the described fixed-bed reactor, catalyst loading pattern is restriction not.
Described oxygenatedchemicals comprise methyl alcohol, dme, ethanol or between them and with any mixture of water, particular methanol, dme or between them and with the mixture of water.
Described dry gas from other production equipments refers to contain but is not limited to the wherein mixed air of one or more components of hydrogen, methane, ethane, ethene, carbon monoxide, carbonic acid gas, nitrogen, the gas of preferred low sulfur content.
Described light olefin component from other production equipment refers to contain but is not limited to the wherein mixed air of one or more components of propylene, butylene, the gas of preferred low sulfur content.
Described other production equipments comprise the devices such as the crude oil secondary processing devices such as coker, hydroeracking unit, viscosity breaking plant and gas sweetening, gas fractionation.
Special-purpose catalyst of the present invention includes the SiO that parts by weight are 1-99%
2/ Al
2O
3For the zeolite with MFI structure in the 20-1000 scope, parts by weight are that binding agent and the parts by weight of 1-70% are the weighting agent of 0-50%;
Described catalyzer contains the phosphorus in oxide compound 0.1-10% weight, the rare earth element of 0.01%-5% weight, and the titanium of 0.01-5% weight, wherein said rare earth element comprises one or more in lanthanum, cerium, the protactinium;
Described binding agent is aluminum oxide, silicon oxide, amorphous aluminum silicide or their mixture;
Described weighting agent is clay and the diatomite such as kaolin, halloysite;
The preparation method of described described special-purpose catalyst comprises the steps:
(1), SiO
2/ Al
2O
3Preparation for the zeolite with MFI structure in the 20-1000 scope
Be about to remove the former powder of organic ZSM-5 zeolite in the duct, through inorganic acid solution after 0.1-5h is processed in room temperature～100 ℃, mix with a kind of colloid that contains phosphorus, rare earth element and titanium, oven dry is 400～700 ℃ of roasting 0.5～10h gained SiO under 0～100% steam atmosphere afterwards
2/ Al
2O
3It is the zeolite with MFI structure in 20～1000 scopes;
Described to remove the mass ratio that the former powder of organic ZSM-5 zeolite mixes with colloid in the duct be zeolite: colloid is 1:0.1 ~ 1;
Described mineral acid is one or more in hydrochloric acid, nitric acid, sulfuric acid, silicofluoric acid or the hydrofluotitanic acid;
The described colloid that contains phosphorus, rare earth element and titanium is that soluble rare-earth salt, solubility titanium salt are dissolved in the deionized water, then adds the P contained compound colloid that forms that stirs; Wherein the mass ratio of soluble rare-earth salt, solubility titanium salt, deionized water and P contained compound is that the mol ratio of P, rare earth element and titanium in the formed colloid is P: rare earth element: titanium is 1:0.03 ~ 3:0.03 ~ 5;
Wherein said soluble rare-earth salt comprises muriate or the nitrate of one or more elements in lanthanum, cerium, the protactinium;
Wherein said solubility titanium salt comprises titanyl sulfate, titanium tetrachloride, titanous chloride, hydrofluotitanic acid or ammonium titanium fluoride;
Wherein said P contained compound comprises phosphoric acid, metaphosphoric acid, tetra-sodium, Secondary ammonium phosphate, primary ammonium phosphate or ammonium phosphate;
(2), the preparation of special-purpose catalyst
With the silicon sol making beating, add kaolin, add again the zeolite with MFI structure of step (1) gained, add again field mountain valley with clumps of trees and bamboo powder, extrusion after the kneading, and place baking oven in 120 ℃ of oven dry 16h, in 550 ℃ of calcination process 4h, namely get special-purpose catalyst of the present invention again;
The amount of the field mountain valley with clumps of trees and bamboo powder that adds satisfies the special-purpose catalyst extruded moulding and gets final product.
Described catalyzer also can be by this area researchist's well-known process granulating and forming.
The reaction conditions of described oxygenate conversion reaction is:
Temperature of reaction is 200-600 ℃, preferred 300-550 ℃; The oxygen-containing compound material preheating temperature is 50 ~ 400 ℃, preferred 100-300 ℃; Oxygen-containing compound material charging air speed 0.2-1000h
-1, preferred 0.5-100h
-1; Reaction pressure is 0.05-5MPa, preferred 0.1-3Mpa.
The condition of described catalyst deactivation is to discharge at the bottom of the gas-liquid separator to detect in the water to contain methyl alcohol, namely carries out the reactor blocked operation, and the inactivation reaction device is regenerated.Regenerative operation is for being that the air of 1-21% passes into reactor and burns by the control oxygen content, and burning temperature is 300-700 ℃, and the charging air speed is 10-10000h
-1
Beneficial effect of the present invention
The present invention transforms the secondary processing device such as existing heavy oil catalytically cracking equipment and oxygenatedchemicals and carries out integratedly, makes the products scheme of catalytic cracking process more flexible, processes raw material more extensive.A kind of method and device that increases catalytically cracked gasoline and productivity of propylene of the present invention, but with the ratio of heavy oil catalytically cracking equipment and the integrated just flexible of oxygenatedchemicals processing unit (plant) catalytic cracking light olefin productive rate and olefin product kind, technique is simple, technology maturation, less investment is easy to realize.Because the primary product that oxygenatedchemicals and light olefin transform is propylene, therefore increased the yield of high-value product propylene; The reactions such as hydrogen transference, cyclisation, aromizing also occur in oxygenatedchemicals and light olefin at the fixed-bed conversion reactor simultaneously, have generated stop bracket gasoline, have therefore not only increased the catalytic cracking process yield of gasoline, have also improved quality of gasoline.Such as embodiment result as seen, mix and refine when accounting for the methyl alcohol of catalytically cracked material amount 80%, can increase propene yield 17.35%, increase yield of gasoline 5.22%, gasoline octane rating increases by 2.7.
The technique of apparatus of the present invention is simple, and the product separation that takes full advantage of catalytic cracking process reclaims technique and Cooling and Heat Source, technology maturation, and less investment is easy to realize.
Description of drawings
The device schematic diagram of Fig. 1, heavy oil fluid catalytic cracking of the prior art
Fig. 2, oxygenatedchemicals process change are produced the device schematic diagram of gasoline and propylene
Fig. 3, integrating heavy oil catalytic cracking with oxygen-containing compound transform the device schematic diagram of producing gasoline and propylene.
Embodiment
The present invention is described in further detail below in conjunction with accompanying drawing and specific embodiment, but do not limit the present invention.
The comparative example 1
Referring to Fig. 1, the device of original heavy oil catalytic cracking process has been described.The reaction-regeneration system operation of heavy oil fluid catalytic cracking comprises, catalytic cracking fresh feed oil 101 through preheating, raw materials used for grand celebration VGO mix the refining 30% vacuum residuum, mix with the recycle stock 102 from freshening oil pump 129, mixing raw material enters riser reactor 104, contact with the regeneration catalyzing cracking catalyst from regenerated catalyst circular route 139 through water vapour 103 air lifts, catalyst system therefor is commercially available CDC catalyzer (trade names, produced by Sinopec catalyzer Chang Ling branch office), reaction conditions is: temperature of reaction is 500 ℃, agent-oil ratio is 6, reaction times 5s, and reaction pressure is 0.2MPa.
The mixture of reaction oil gas and catalyzer enters settling vessel 105 at leg outlet behind the gas-solid sharp separation, the catalyzer of carbon deposit falls to entering stripping stage 106, enter revivifier 136 through the reclaimable catalyst behind water vapour 107 strippings through circular route to be generated, contact with air that main air blower 137 enters revivifier through main air line 138 and to burn, burn flue gas 140 and remove smoke energy recovering system.
The catalytic cracking reaction oil gas that settling vessel 105 ejects enters separation column 109 bottoms through main In Oil-gas Line 108, and after oil-slurry pump 131 entered strainer 132, part was returned separation column through 133 lines to the Fractionator Bottom slurry oil through 130 lines, and part is as product slurry oil 134 outer getting rid of.
Referring to Fig. 2, oxygenatedchemicals process change of the present invention is produced the device of gasoline and propylene, oxygenatedchemicals fresh feed 201, comprise methyl alcohol, dme, ethanol or between them and with any mixture of water, entering fixed-bed conversion set of reactors 203 tops after interchanger 202 heats up contacts with special-purpose catalyst, other has device top rich gas 113 unstripped gass from original catalytic cracking fractionating tower 109 top oil gas gas-liquid separators 112, from coker, the sweet dry gas of hydroeracking unit etc. crude oil secondary processing device and/or the 205 unstripped gas segmentations of light olefin component enter fixed-bed conversion set of reactors 203 middle parts and contact with special-purpose catalyst, set of reactors is the combination of 2-5 fixed-bed reactor, when single catalyst reactor is regenerated because of inactivation, still have other reactors to carry out conversion reaction so that production is carried out continuously; Set of reactors reaction oil gas 206 out enters gas-liquid separator 208 behind water cooler 207, condensate draining 209 at the bottom of the device, and device pushes up compressed machine 212 superchargings of uncooled rich gas and becomes supercharging rich gas 213 and former catalytic cracking supercharging rich gas 115 to be mixed into the absorbing-stabilizing system that the rich gas product goes former catalytic cracking unit; The gas-liquid separator middle part is extracted raw gasline 211 out through raw gasline pump 210 and is mixed into the absorbing-stabilizing system that the raw gasline product goes former catalytic cracking unit with former catalytic cracking raw gasline 118.
Embodiment 1
Fig. 3 is that integrating heavy oil catalytic cracking with oxygen-containing compound transforms the device schematic diagram of producing gasoline and propylene.Illustrate that in conjunction with Fig. 3 heavy oil fluid catalytic cracking of the present invention and methanol conversion only transform an embodiment of the integrated technique of methyl alcohol.
The reaction-regeneration system operation of original heavy oil fluid catalytic cracking is constant, shown in comparative example 1.
Oxygenatedchemicals fresh feed 201 of the present invention is that thick methyl alcohol is (commercially available, moisture 20% weight), entering fixed-bed conversion set of reactors 203 tops after after interchanger 202 is warming up to 200 ℃ contacts with special-purpose catalyst A, the methanol feeding amount is 0.85 with the ratio of catalytically cracked stock, set of reactors is the combination of 2-5 fixed-bed reactor, when single catalyst reactor is regenerated because of inactivation, still have other reactors to carry out conversion reaction so that production is carried out continuously; Set of reactors reaction oil gas 206 out enters gas-liquid separator 208 behind water cooler 207, condensate draining 209 at the bottom of the device, and device pushes up the compressed machine of uncooled rich gas 212 rear one-tenth supercharging rich gases 213 and is mixed into the rich gas product with former catalytic cracking supercharging rich gas 115 and removes absorbing-stabilizing system; The gas-liquid separator middle part is extracted out through raw gasline pump 210 and is removed absorbing-stabilizing system after raw gasline 211 is mixed into the raw gasline product with former catalytic cracking raw gasline 118.The reaction conditions of used methanol conversion sees Table 1.The integrated reaction products therefrom is through unified metering, and it is basic calculation according to catalytically cracked stock all that products therefrom distributes.
Methanol conversion special-purpose catalyst A's is composed as follows: contain SiO
2/ Al
2O
3Be 180 ZSM-5 zeolite 70%, press SiO
2The silica sol binder 25% of meter, kaolin 5%; Its preparation method is as follows:
With SiO
2/ Al
2O
3Be that 180 ZSM-5 zeolite (the Sinopec catalyzer is built long branch office product) takes off amine 550 ℃ of roastings and processes 4h, get by butt and take off amine zeolite 4kg, add the making beating of 24kg deionized water, adding concentration and be 31% hydrochloric acid, to regulate slurry pH value be 1.5, be warming up to 70 ℃ and keep 1h, filter, wash to get molecule sieving cake.With 70 gram La (NO
3)
36H
2O is dissolved in the 1000 gram deionized waters, stirs the lower 20 gram TiOSO that add
4, add again 130 gram NH
4H
2PO
4, the above-mentioned molecular sieve filter cake making beating of the rear adding that stirs is evenly dried, and places retort furnace at 550 ℃ of calcination process 3h, the Wessalith CS that must have the MFI structure;
With silicon sol (commercially available trade mark JN30, SiO
2Content is 30%) the 2.5kg making beating, add butt meter 150 gram kaolin (China Kaolin Co., Ltd's product), add again the Wessalith CS that butt meter 2.1Kg has the MFI structure; Add again 150 gram field mountain valley with clumps of trees and bamboo powder (commercially available prod), extrusion after the kneading, the catalyzer bar places baking oven in 120 ℃ of oven dry 16h, again in 550 ℃ of calcination process 4h, namely gets special-purpose catalyst A of the present invention.During catalyst elements forms, with P
2O
5Meter phosphorus content 1.37% is with La
2O
3Meter La content 0.45% is with TiO
2Meter Ti content is 0.15%.
The condition of the described catalyst deactivation of the present embodiment regeneration is to detect in the condensate draining 209 at the bottom of gas-liquid separator 208 devices to contain methyl alcohol, namely carries out the reactor blocked operation, and the inactivation reaction device is regenerated.Regenerative operation is for to burn by air.
Embodiment 2
Fig. 3 is that integrating heavy oil catalytic cracking with oxygen-containing compound transforms the device schematic diagram of producing gasoline and propylene.In conjunction with Fig. 3 explanation, according to integrated technique technology of the present invention, methanol conversion transforms the integrated operating mode of methyl alcohol, partially catalyzed cracking rich gas and sweet dry gas.
The reaction-regeneration system operation of original heavy oil fluid catalytic cracking is constant, shown in comparative example 1.
Oxygenatedchemicals fresh feed 201 of the present invention is that thick methyl alcohol is (commercially available, moisture 20% weight), entering fixed-bed conversion set of reactors 203 tops after after interchanger 202 is warming up to 300 ℃ contacts with special-purpose catalyst B, the methanol feeding amount is 0.5 with the ratio of catalytically cracked stock, set of reactors is the combination of 2-5 fixed-bed reactor, when single catalyst reactor is regenerated because of inactivation, still have other reactors to carry out conversion reaction so that production is carried out continuously; 50% part of device top rich gas 113 flows of original catalytic cracking fractionating tower 109 top oil gas gas-liquid separators 112 enters oxygenatedchemicals fixed-bed reactor 203 as reaction raw materials 204, it is hydrogen 1.8%, carbonic acid gas 3.9%, methane 4.86%, ethane 4.88%, ethene 6.0% by mass that this rich gas forms, propane 5.69%, propylene 23.61%, butane 26.09%, butylene 22.80%, C5+ hydro carbons 0.36%.Other has the partial desulfurization dry gas 205 introducing methanol conversion from fuel gas system, it is hydrogen 5.64%, carbonic acid gas 12.21%, methane 15.23%, ethane 18.79%, ethene 16.90% by mass that dry gas forms, propane 1.39%, dry gas incorporation are 5% of catalytically cracked stock.
Set of reactors reaction oil gas 206 out enters gas-liquid separator 208 behind water cooler 207, condensate draining 209 at the bottom of the device, and device pushes up the compressed machine of uncooled rich gas 212 rear one-tenth supercharging rich gases 213 and is mixed into the rich gas product with former catalytic cracking supercharging rich gas 115 and removes absorbing-stabilizing system; The gas-liquid separator middle part is extracted out through raw gasline pump 210 and is removed absorbing-stabilizing system after raw gasline 211 is mixed into the raw gasline product with former catalytic cracking raw gasline 118.The reaction conditions of used methanol conversion sees Table 1.The unified metering of integrated reaction products therefrom, it is basic calculation according to catalytically cracked stock all that products therefrom distributes.
Methanol conversion special-purpose catalyst composed as follows: contain SiO
2/ Al
2O
3Be 60 ZSM-5 zeolite 60%, press Al
2O
3The alumina binder 40% of meter; Its preparation method is as follows.
With SiO
2/ Al
2O
3Be that 60 ZSM-5 zeolite (the Sinopec catalyzer is built long branch office product) takes off amine zeolite 4kg by butt, add the making beating of 24kg deionized water, add again the making beating of 2kg ammonium chloride, be warming up to 70 ℃ and keep 1h, filter, wash to get molecule sieving cake.With 50 gram La (NO
3)
36H
2O is dissolved in the 1000 gram deionized waters, stirs the lower 220 gram TiOSO that add
4, add again 115 gram H
3PO
4(concentration 85%), the making beating of the above-mentioned molecular sieve filter cake of the rear adding that stirs evenly, oven dry, place rotary roasting furnace under 100% steam atmosphere, 550 ℃ of calcination process 2h, the zeolite B that must have the MFI structure.
The zeolite B that butt meter pseudo-boehmite powder (Chalco Shandong Aluminum Plant product) 1.2kg and butt meter 1.8Kg is had the MFI structure is dry mixed, and adds 150 gram field mountain valley with clumps of trees and bamboo powder and 500 gram deionized waters mix again, and adds extrusion after the 120 gram nitric acid kneadings again.The catalyzer bar places baking oven in 120 ℃ of oven dry 16h, again in 500 ℃ of calcination process 4h, namely gets special-purpose catalyst B of the present invention.During catalyst elements forms, with P
2O
5Meter phosphorus content 1.07% is with La
2O
3Meter La content 0.25% is with TiO
2Meter Ti content is 1.65%.
The condition of the described catalyst deactivation of the present embodiment regeneration is to detect in the condensate draining 209 at the bottom of gas-liquid separator 208 devices to contain methyl alcohol, namely carries out the reactor blocked operation, and the inactivation reaction device is regenerated.Regenerative operation is for to burn by air.
Embodiment 3
Fig. 3 is that integrating heavy oil catalytic cracking with oxygen-containing compound transforms the device schematic diagram of producing gasoline and propylene.In conjunction with Fig. 3 explanation, according to integrated technique technology of the present invention, methanol conversion transforms the integrated operating mode of methyl alcohol, partially catalyzed cracking rich gas and sweet dry gas.
The operation of the reaction-regeneration system of original heavy oil fluid catalytic cracking is constant, as to shown in embodiment 1 ratio.
Oxygenatedchemicals fresh feed 201 of the present invention is that thick methyl alcohol is (commercially available, moisture 20% weight), entering fixed-bed conversion set of reactors 203 tops after after interchanger 202 is warming up to 300 ℃ contacts with special-purpose catalyst C, the methanol feeding amount is 0.5 with the ratio of catalytically cracked stock, set of reactors is the combination of 2-5 fixed-bed reactor, when single catalyst reactor is regenerated because of inactivation, still have other reactors to carry out conversion reaction so that production is carried out continuously; 50% part of device top rich gas 113 flows of original catalytic cracking fractionating tower 109 top oil gas gas-liquid separators 112 enters oxygenatedchemicals fixed-bed reactor 203 as reaction raw materials 204, it is hydrogen 1.8%, carbonic acid gas 3.9%, methane 4.86%, ethane 4.88%, ethene 6.0% by mass that this rich gas forms, propane 5.69%, propylene 23.61%, butane 26.09%, butylene 22.80%, C5+ hydro carbons 0.36%.Other has the partial desulfurization dry gas 205 introducing methanol conversion from fuel gas system, it is hydrogen 5.64%, carbonic acid gas 12.21%, methane 15.23%, ethane 18.79%, ethene 16.90% by mass that dry gas forms, propane 1.39%, dry gas incorporation are 5% of catalytically cracked stock.Also have C4 light olefin component and sweet dry gas from the gas fractionation system to be mixed into unstripped gas 205 introducing methanol conversion, this fractions consisting is 0.73% for butylene 52.97%, butane 46.30%, C5+ hydro carbons by mass, and the C 4 fraction incorporation is 5% of catalytically cracked stock.Set of reactors reaction oil gas 206 out enters gas-liquid separator 208 behind water cooler 207, condensate draining 209 at the bottom of the device, and device pushes up the compressed machine of uncooled rich gas 212 rear one-tenth supercharging rich gases 213 and is mixed into the rich gas product with former catalytic cracking supercharging rich gas 115 and removes absorbing-stabilizing system; The gas-liquid separator middle part is extracted out through raw gasline pump 210 and is removed absorbing-stabilizing system after raw gasline 211 is mixed into the raw gasline product with former catalytic cracking raw gasline 118.The reaction conditions of used methanol conversion sees Table 1.The unified metering of integrated reaction products therefrom, it is basic calculation according to catalytically cracked stock all that products therefrom distributes.
Methanol conversion special-purpose catalyst C's is composed as follows: contain SiO
2/ Al
2O
3Be 240 ZSM-5 zeolite 70%, by SiO
2Silica sol binder 20%, the kaolin 10% of meter; Its preparation method is as follows.
With SiO
2/ Al
2O
3Be that 240 ZSM-5 zeolite (Nankai's catalyst plant product) takes off amine 550 ℃ of roastings and processes 4h, get by butt and take off amine zeolite 4kg, add the making beating of 24kg deionized water, adding concentration and be 31% hydrochloric acid, to regulate slurry pH value be 1.5, be warming up to 70 ℃ and keep 1h, filter, wash to get molecule sieving cake.With 18 gram CeCl
37H2O is dissolved in the 1000 gram deionized waters, stirs the lower 65 gram TiOSO that add
4, add again 60 gram H
3PO
4(concentration 85%), the above-mentioned molecular sieve filter cake making beating of the rear adding that stirs is evenly dried, and places retort furnace in 550 ℃ of calcination process 4h, must have the zeolite C of MFI structure.
With silicon sol 2.0kg making beating, add butt meter 300 gram kaolin, add again the zeolite C that butt meter 2.1Kg has the MFI structure, add again 150 gram field mountain valley with clumps of trees and bamboo powder (commercially available prod), extrusion after the kneading.The catalyzer bar places baking oven in 120 ℃ of oven dry 16h, again in 500 ℃ of calcination process 4h, namely gets special-purpose catalyst C of the present invention.During catalyst elements forms, with P
2O
5Meter phosphorus content 0.57% is with CeO
2Meter Ce content 0.25% is with TiO
2Meter Ti content is 0.55%.
The condition of the described catalyst deactivation of the present embodiment regeneration is to detect in the condensate draining 209 at the bottom of gas-liquid separator 208 devices to contain methyl alcohol, namely carries out the reactor blocked operation, and the inactivation reaction device is regenerated.Regenerative operation is for to burn by air.
From table 1 result as seen, the propene yield of independent heavy oil catalytic cracking process is on the low side, gasoline octane rating is also on the low side.After adopting integrated technique, owing to having adjusted neatly methyl alcohol and refinery's gas raw material, so that distributing, catalytic cracking production can adjust flexibly, with the reaction of methanol conversion device material composition change, propylene and the gasoline yield of integrated technique all are significantly increased, wherein propylene has increased respectively 17.39%, 2.25% and 7.76%, gasoline has increased respectively 5.22%, 12.31% and 4.08%, aromaticity content was high during the gasoline that obtains owing to methanol conversion simultaneously formed, so that gained catalytic gasoline octane value also significantly improves, improved respectively 2.7,4.0 and 2.7, octane value all is higher than 90, thereby improves quality of gasoline.
Claims (10)
1. an integrating heavy oil catalytic cracking with oxygen-containing compound transforms the system that produces gasoline and propylene, comprises catalytic cracking unit, characterized by further comprising the oxygenatedchemicals processing unit (plant);
Wherein said catalytic cracking unit comprises separation column and gas-liquid separator;
Described oxygenatedchemicals processing unit (plant) comprises a row fixed-bed reactor group, gas-liquid separator and heat-exchange system; The fixed-bed reactor outlet enters the gas-liquid separator of oxygenatedchemicals processing unit (plant) behind heat-exchange system;
The gas tube at the gas-liquid separator top at the separation column top of described catalytic cracking unit is drawn side line to the feeding part of a row fixed-bed reactor group of oxygenatedchemicals processing unit (plant), to realize the integrated of two covering devices; Oxygenatedchemicals after vaporization enters a fixed-bed reactor group of equipping special-purpose catalyst and carries out conversion reaction, simultaneously draw the feeding part that side line enters into a row fixed-bed reactor group of oxygenatedchemicals processing unit (plant) from the part rich gas component of the gas-liquid separator of the fractionation cat head of catalytic cracking unit through above-mentioned, with the dry gas from other production equipments, the segmentation of light olefin component enter above-mentioned fixed-bed reactor group contact with above-mentioned special-purpose catalyst carry out conversion reaction and finish after, fixed-bed reactor outlet oil gas enters the gas-liquid separator of oxygenatedchemicals processing unit (plant) after the heat-exchange system cooling, the rich gas that the gas-liquid separator of oxygenatedchemicals processing unit (plant) ejects mixes the absorbing-stabilizing system of catalytic cracking unit with former catalytic cracking supercharging rich gas after supercharging, the gas-liquid separator stage casing of oxygenatedchemicals processing unit (plant) is extracted raw gasline out and is mixed the absorbing-stabilizing system of catalytic cracking unit with former catalytic cracking raw gasline, discharges the additional circulating water system that enters of water at the bottom of the gas-liquid separator of oxygenatedchemicals processing unit (plant);
Described other production equipments comprise coker, hydroeracking unit, viscosity breaking plant and gas sweetening, gas fractionation plant.
2. a kind of integrating heavy oil catalytic cracking with oxygen-containing compound as claimed in claim 1 transforms the system that produces gasoline and propylene, it is characterized in that a described row fixed-bed reactor group is that 2-5 fixed-bed reactor are connected in series or in parallel.
3. an integrating heavy oil catalytic cracking with oxygen-containing compound transforms the method for producing gasoline and propylene, it is characterized in that as follows: take refinery catalytic cracking fractionating tower top oil-gas separator part rich gas component and from dry gas, light olefin component and the organic oxygen-containing compound of other crude oil secondary processing production equipment as raw material, adopt one group of fixed-bed reactor, preparing propone and gasoline under the effect of special-purpose catalyst;
The quality proportioning of each above-mentioned feed composition reaction is part rich gas component: dry gas: light olefin component: organic oxygen-containing compound is 0～10:0～10:0～10:1;
Described catalytic reaction condition: 200～600 ℃ of temperature of reaction, 50～400 ℃ of the preheating temperatures of oxygenatedchemicals, oxygenate feedstock air speed 0.2～1000h
-1, reaction pressure 0.05～5Mpa;
Described organic oxygen-containing compound be methyl alcohol, dme, ethanol or between them and with any mixture of water;
The typical moiety of described rich gas component comprises hydrogen, methane, ethene, ethane, propane, propylene, butylene, butane and a small amount of C5 hydro carbons, carbonic acid gas, hydrogen sulfide;
Described dry gas component from other production equipments, its typical moiety comprise hydrogen, methane, ethene, ethane and a small amount of propane, propylene, carbonic acid gas, nitrogen;
Described light olefin component from other production equipments refers to the component that contains C4 alkene, C5 alkene through gas fractionation plant production;
Described other production equipments comprise coker, hydroeracking unit, viscosity breaking plant crude oil secondary processing device and gas sweetening, gas fractionation plant;
Described special-purpose catalyst includes the SiO that parts by weight are 60-70%
2/ Al
2O
3For the zeolite with MFI structure in the 20-1000 scope, parts by weight are that binding agent and the parts by weight of 1-40% are the weighting agent of 0-10%; Contain the phosphorus in oxide compound 0.1-10% weight in the described catalyzer, the rare earth element of 0.01%-5% weight, the titanium of 0.01-5% weight, wherein said
Rare earth element comprises one or more in lanthanum, cerium, the protactinium;
Described binding agent is aluminum oxide, silicon oxide, amorphous aluminum silicide or their mixture;
Described weighting agent comprises kaolin, halloysite and diatomite;
Described SiO
2/ Al
2O
3For the zeolite preparation method with MFI structure in the 20-1000 scope comprises the steps: to be about to remove organic SiO in the duct
2/ Al
2O
3Be the former powder of the ZSM-5 zeolite of 20-1000, through inorganic acid solution after 0.1-5h is processed in room temperature～100 ℃, mix with a kind of colloid that contains phosphorus, rare earth element and titanium, oven dry is 400～700 ℃ of roasting 0.5～10h gained SiO under 0～100% steam atmosphere afterwards
2/ Al
2O
3It is the zeolite with MFI structure in 20～1000 scopes;
The former powder of described ZSM-5 zeolite is when mineral acid treatment, and keeping molecular sieve pulp pH value is 0.5-5;
Described mineral acid is one or more in hydrochloric acid, nitric acid, sulfuric acid, silicofluoric acid or the hydrofluotitanic acid;
The described colloid that contains phosphorus, rare earth element and titanium is that soluble rare-earth salt, solubility titanium salt are dissolved in the deionized water, then adds the P contained compound colloid that forms that stirs; The mol ratio 1:0.03 of P, rare earth element and titanium ~ 3:0.03 ~ 5 in the colloid that forms of P contained compound, soluble rare-earth salt, solubility titanium salt and deionized water wherein;
Wherein said soluble rare-earth salt comprises muriate or the nitrate of one or more elements in lanthanum, cerium, the protactinium;
Wherein said solubility titanium salt comprises titanyl sulfate, titanium tetrachloride, titanous chloride, hydrofluotitanic acid, ammonium titanium fluoride;
Wherein said P contained compound comprises phosphoric acid, metaphosphoric acid, tetra-sodium, Secondary ammonium phosphate, primary ammonium phosphate and ammonium phosphate.
4. method according to claim 3 is characterized in that, described oxygenatedchemicals is preferably methyl alcohol.
5. according to claim 3 or 4 described methods, it is characterized in that the condition of catalyzed reaction: 300～550 ℃ of temperature of reaction; 100～350 ℃ of the preheating temperatures of oxygenatedchemicals; Oxygenate feedstock air speed 0.5～100h
-1Reaction pressure 0.1～3MPa.
6. according to claim 3 or 4 described methods, it is characterized in that the condition of catalyzed reaction: preferred 500 ℃ of temperature of reaction; Preferred 200～300 ℃ of the preheating temperature of oxygenatedchemicals; Preferred 1.0～the 10.8h of oxygenate feedstock air speed
-1Preferred 0.11～the 0.3Mpa of reaction pressure.
7. special-purpose catalyst described in claim 3 or 4 described methods is characterized in that described special-purpose catalyst composition contains SiO
2/ Al
2O
3Be 180 ZSM-5 zeolite 70%, press SiO
2The silica sol binder 25% of meter, kaolin 5%; During catalyst elements forms, with P
2O
5Meter phosphorus content 1.37% is with La
2O
3Meter La content 0.45% is with TiO
2Meter Ti content is 0.15%;
Described special-purpose catalyst, its preparation method is as follows:
With SiO
2/ Al
2O
3Be that 180 ZSM-5 zeolite takes off amine 550 ℃ of roastings and processes 4h, get by butt and take off amine zeolite 4kg, add the making beating of 24kg deionized water, adding concentration and be 31% hydrochloric acid, to regulate slurry pH value be 1.5, is warming up to 70 ℃ and keeps 1h, filters, and washes to get molecule sieving cake;
With 70 gram La (NO
3)
36H
2O is dissolved in the 1000 gram deionized waters, stirs the lower 20 gram TiOSO that add
4, add again 130 gram NH
4H
2PO
4, the above-mentioned molecular sieve filter cake making beating of the rear adding that stirs is evenly dried, and places retort furnace at 550 ℃ of calcination process 3h, the zeolite that must have the MFI structure;
With SiO
2Content is 30% silicon sol 2.5kg making beating, add butt meter 150 gram kaolin, the zeolite that adds again the above-mentioned MFI of the having structure of butt meter 2.1Kg, add again 150 gram field mountain valley with clumps of trees and bamboo powder, extrusion after the kneading, the catalyzer bar places baking oven in 120 ℃ of oven dry 16h, in 550 ℃ of calcination process 4h, namely gets the invention described above special-purpose catalyst again.
8. special-purpose catalyst described in claim 3 or 4 described methods is characterized in that the composition of described special-purpose catalyst contains SiO
2/ Al
2O
3Be 60 ZSM-5 zeolite 60%, press Al
2O
3The alumina binder 40% of meter; During catalyst elements forms, with P
2O
5Meter phosphorus content 1.07% is with La
2O
3Meter La content 0.25% is with TiO
2Meter Ti content is 1.65%;
Described special-purpose catalyst, its preparation method is as follows:
With SiO
2/ Al
2O
3Be that 60 ZSM-5 zeolite takes off amine zeolite 4kg by butt, add the making beating of 24kg deionized water, add again the making beating of 2kg ammonium chloride, be warming up to 70 ℃ and keep 1h, filter, wash to get molecule sieving cake;
With 50 gram La (NO
3)
36H
2O is dissolved in the 1000 gram deionized waters, stirs the lower 220 gram TiOSO that add
4, adding 115 gram concentration is 85% H again
3PO
4, the making beating of the above-mentioned molecular sieve filter cake of the rear adding that stirs evenly, oven dry, place rotary roasting furnace under 100% steam atmosphere, 550 ℃ of calcination process 2h, the zeolite that must have the MFI structure;
The zeolite of butt meter pseudo-boehmite powder 1.2kg and the above-mentioned MFI of the having structure of butt meter 1.8Kg is dry mixed, add again 150 gram field mountain valley with clumps of trees and bamboo powder and 500 gram deionized waters mixing, add again extrusion after the 120 gram nitric acid kneadings, the catalyzer bar places baking oven in 120 ℃ of oven dry 16h, in 500 ℃ of calcination process 4h, namely get the invention described above special-purpose catalyst again.
9. special-purpose catalyst described in claim 3 or 4 described methods is characterized in that described special-purpose catalyst contains SiO
2/ Al
2O
3Be 240 ZSM-5 zeolite 70%, by SiO
2Silica sol binder 20%, the kaolin 10% of meter; During catalyst elements forms, with P
2O
5Meter phosphorus content 0.57% is with CeO
2Meter Ce content 0.25% is with TiO
2Meter Ti content is 0.55%;
Described special-purpose catalyst, its preparation method is as follows:
With SiO
2/ Al
2O
3Be that 240 ZSM-5 zeolite takes off amine 550 ℃ of roastings and processes 4h, get by butt and take off amine zeolite 4kg, add the making beating of 24kg deionized water, adding concentration and be 31% hydrochloric acid, to regulate slurry pH value be 1.5, is warming up to 70 ℃ and keeps 1h, filters, and washes to get molecule sieving cake;
With 18 gram CeCl
37H2O is dissolved in the 1000 gram deionized waters, stirs the lower 65 gram TiOSO that add
4, add again 60 grams and be the H of concentration 85%
3PO
4, the above-mentioned molecular sieve filter cake making beating of the rear adding that stirs is evenly dried, and places retort furnace in 550 ℃ of calcination process 4h, the zeolite that must have the MFI structure;
Silicon sol 2.0kg is pulled an oar, add butt meter 300 gram kaolin, the zeolite that adds again the above-mentioned MFI of the having structure of butt meter 2.1Kg, add again 150 gram field mountain valley with clumps of trees and bamboo powder, extrusion after the kneading, the catalyzer bar places baking oven in 120 ℃ of oven dry 16h, in 500 ℃ of calcination process 4h, namely gets the invention described above special-purpose catalyst again.
10. according to claim 3 or 4 described methods, it is characterized in that: the condition of described catalyst deactivation is to discharge to detect in the water at the bottom of the gas-liquid separator to contain methyl alcohol, namely carries out the reactor blocked operation, and the inactivation reaction device is regenerated;
Regenerative operation for be 1 by the control oxygen content～
21%Air pass into reactor and burn, burning temperature is 300～700 ℃, the charging air speed is 10～10000h
-1
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| CN102492465B (en) * | 2011-11-29 | 2014-05-07 | 中国科学院大连化学物理研究所 | Method for producing vehicle fuel from low carbon hydrocarbon rich in alkene and oxygen-containing compound |
| CN104056653B (en) * | 2013-03-22 | 2016-09-07 | 中国石油化工股份有限公司 | A kind of catalyst for producing propylene with methanol |
| CN104056654B (en) * | 2013-03-22 | 2016-07-06 | 中国石油化工股份有限公司 | A kind of ZSM-5 molecular sieve compositions, preparation method and application thereof |
| CN109092287A (en) * | 2017-06-21 | 2018-12-28 | 中国石油化工股份有限公司 | Selective acetylene hydrocarbon hydrogenation catalyst |
| CN114989865B (en) * | 2022-05-26 | 2024-01-30 | 中科合成油技术股份有限公司 | Method for producing low-carbon olefin by coupling Fischer-Tropsch synthetic oil with low-carbon alcohol ether oxygen-containing compound |
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| DE102005029399B4 (en) * | 2005-06-24 | 2015-03-05 | Air Liquide Global E&C Solutions Germany Gmbh | Process and plant for the production of C2-C4 olefins from methanol and / or dimethyl ether with increased yield |
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