CN101205172B

CN101205172B - Method for producing dimethyl ether by fluidized catalytic gas-phase dehydration of methanol

Info

Publication number: CN101205172B
Application number: CN2006101695111A
Authority: CN
Inventors: 毛安国; 朱根权; 谢朝钢; 孙新; 孙益群; 龙军; 张久顺; 宗保宁
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2006-12-22
Filing date: 2006-12-22
Publication date: 2011-04-20
Anticipated expiration: 2026-12-22
Also published as: CN101205172A

Abstract

The invention relates to a method for producing a dimethyl ether by applying the fluidization, catalysis and gas phase dehydration to a methanol. The methanol serving as the raw materials contacts with the catalysts in which the Y series is contained in a reactor provided with a riser and a fluidized bed and the reaction between the methanol and the catalysts is carried out on the conditions that the temperature ranges from 150 to 350 DEG C, the weight ratio of the catalysts to the methanol raw materials ranges from 0.001 to 50, the reaction time ranges from 0.1 to 20 seconds and the pressure ranges from 1 to 1000kPa; the bed temperature of the fluidized bed reactor is controlled to be below 350 DEG C and the reactants are separated so as to obtain the coked catalysts and the target products, dimethyl ether; the coked catalysts separated out from a cyclone separator are circulated back to the fluidized bed and part or all of the coked catalysts in the fluidized bed are enter a generator to be subject to the coke burning regeneration with or without being stripped; the regenerated catalysts go back into the reactor so as to contact with the methanol raw materials. The method effectively controls the bed reaction temperature and ensures that the methanol is continuously converted into the dimethyl ether, the conversion rate of the methanol is usually higher than 80 per cent and the selectivity of the dimethyl ether is more than 98 per cent.

Description

A kind of method of producing dimethyl ether by fluidized catalytic gas-phase dehydration of methanol

Technical field

The present invention relates to a kind of method from the methanol production dme.

Background technology

The production method of dme (DME) has single stage method and two step method.Single stage method is meant by dimethyl ether synthesis of unstripped gas; Two step method is by the synthetic gas synthesizing methanol, and then dimethyl ether preparation by dehydrating.

Two step method is carried out in two steps, and promptly earlier by the synthetic gas synthesizing methanol, methyl alcohol is dewatering preparing dimethy ether under acid catalysis.The two step method dimethyl ether synthesis is the main technique that at present domestic and international dme is produced, this method is raw material with the refined methanol, the dehydration reaction by product is few, dme purity height, technical maturity, the device wide adaptability, aftertreatment is simple, can directly build methanol production factory in, also can build the good non-methanol production factory of other public utility in.The both at home and abroad employing contains γ-Al more ₂O ₃/ SiO ₂The ZSM-5 molecular sieve of making is as dehydration catalyst.Temperature of reaction is controlled at 280-340 ℃, and pressure is 0.5-0.8MPa.The per pass conversion of methyl alcohol is between 70-85%, and the selectivity of dme is greater than 98%.

CN1180064A discloses a kind of production method of dme, is raw material with methyl alcohol, reacts dehydration under lesser temps (100 to 125 ℃), normal pressure (0-0.05MPa gauge pressure) and new catalyst action, can the output gas of dimethyl ether.

CN1125216A discloses a kind of method by the methanol production dme, this method is that methyl alcohol is introduced into the vaporization knockout tower, after removing high boiling product and impurity, in multistage cold shock formula reactor, composite solid-acid catalyst carries out catalytic and dehydration reaction under existing, and dewatered product enters and carries out rectifying in the high efficiency packing rectifying tower, according to different needs, select the different operating reflux ratio, make purity 90-99.99% dme product.

CN1368493A discloses a kind of method of preparing bimethyl ether by catalytic dewatering of methanol, relates to a kind of method of methyl alcohol catalytic dehydration preparing dimethy ether, and wherein dehydration is to contain SO ₄ ^2-Solid acid catalyst exist and to carry out down.SO in the catalyzer ₄ ^2-Content is preferably the heavy % of 2-25, and preferred support of the catalyst is selected from γ-Al ₂O ₃, η-Al ₂O ₃And SiO ₂

CN1301686A discloses a kind of method of dimethyl ether by methanol dehydration, and this method is to be raw material with kaolin, as catalyzer, is used for dimethyl ether by methanol dehydration after sulfuric acid modified.

US2004/0034255A1 has announced a kind of method of utilizing activated alumina catalysis methanol gas-phase dehydration to prepare dme, the aperture of described activated alumina be 2.5nm to 8.0nm, wherein the content of sodium oxide is lower than 0.07%.

Aforesaid method mainly utilizes catalysis methanol dehydration dimethyl ether-preparings such as compound solid-acid, sour modified kaolin, activated alumina, and mainly utilizes fixed-bed reactor, and how the dme of production is as fine chemicals, and industrial scale is little, and production cost is higher.In addition, the dehydration reaction heat release of methyl alcohol, bed temperature is difficult to control.

Summary of the invention

The objective of the invention is to provide on the basis of existing technology a kind of method of producing dimethyl ether by fluidized catalytic gas-phase dehydration of methanol.

Technical scheme of the present invention is as follows:

Methanol feedstock contacts in riser tube+fluidized-bed reactor with the catalyzer that contains the Y series zeolite, be 0.001～50 in the weight ratio of 150～350 ℃ of temperature, catalyzer and methanol feedstock, react under the condition of reaction times 0.1-20 second, pressure 1～1000kPa, by heat collector being set in fluidized reactor bed inside; And/or the partial product Pd/carbon catalyst comes out from fluidized-bed reactor bed top, loops back the riser tube of fluidisation reactor bed bottom through outside heat removing, and carbon deposited catalyst is through stripping or without stripping in the working cycle; And/or regenerated catalyst returns the riser tube of fluidized reactor bed bottom through outside heat removing or interior heat-obtaining, and controlling flow fluidized bed reactor bed temperature is below 350 ℃, and reactant flow obtains carbon deposited catalyst and purpose product dme through separation; The carbon deposited catalyst of separating from cyclonic separator loops back the fluidisation bed, and the carbon deposited catalyst in the fluidized-bed is partly or entirely through stripping or enter revivifier without stripping and carry out coke burning regeneration, and the regenerated catalyst Returning reactor contacts with methanol feedstock.

Because the dehydration reaction very exothermic of methyl alcohol, bed temperature are difficult to control.In order to control the fluidisation reactor batch temperature, take in the following measures one or more below 350 ℃:

1, in fluidized reactor bed inside heat collector is set;

2, the partial product Pd/carbon catalyst comes out from fluidized reactor bed top, loops back the riser tube of fluidisation reactor bed bottom through outside heat removing, and carbon deposited catalyst is through stripping or without stripping in the working cycle;

3, regenerated catalyst returns the riser tube of fluidized reactor bed bottom through outside heat removing or interior heat-obtaining.

Entry position when regenerated catalyst and carbon deposited catalyst cycle back to riser tube is identical or different, if the position difference, preferably the inlet of carbon deposited catalyst is in the regenerated catalyst bottom that enters the mouth.

Described cyclonic separator is 1 grade or 2 grades.

The content of methyl alcohol is the more preferably heavy % of 90-100 of the heavy % of the preferred 50-100 of the heavy % of 5-100 in the methanol feedstock of the present invention, can contain small amount of impurities such as water etc.Described methanol feedstock through gasification, the synthetic thick methyl alcohol that makes, also can be the methyl alcohol in other source from various fossil oils such as Sweet natural gas, coal, oil-sand, oil etc.Methyl alcohol can liquid phase feeding among the present invention, also can with reaction product or the laggard promoting the circulation of qi of other thermal source heat exchanges charging mutually.

The catalyzer of the described Y of containing series zeolite can be Y series zeolite and other the optional molecular sieve that does not contain inorganic oxide and clay, and wherein the weight ratio of other molecular sieve and Y series zeolite is 0-10; Preferably contain the Y series zeolite of inorganic oxide, clay and other optional molecular sieve, wherein the weight ratio of other molecular sieve and Y series zeolite is 0-10, and other molecular sieve and Y series zeolite sum account for the heavy % of 10-80 of total catalyst weight.

Wherein the Y series zeolite comprises the Y type and derives or modified zeolite, is selected from one or more the mixture among Y, HY, REY, REHY, USY, the REUSY.

Described other molecular screening one or more in mesopore zeolite, Beta zeolite, SAPO molecular sieve.

Mesopore zeolite comprises ZRP series (rare earth modified), ZSP series (iron modification), ZSM series zeolite and derives or modified zeolite, the more detailed description of relevant ZRP is referring to US5,232,675, the ZSM series zeolite is selected from one or more the mixture among the zeolite of ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM-38, ZSM-48 and other similar structures, the more detailed description of relevant ZSM-5 is referring to US3, and 702,886.

More excellent catalyzer contains Y series zeolite, mesopore zeolite, inorganic oxide and clay, and wherein the weight ratio of mesopore zeolite and Y series zeolite is 0.1-10, and mesopore zeolite and Y series zeolite sum account for the heavy % of 10-80 of total catalyst weight.

Described inorganic oxide is selected from one or more the mixture in aluminum oxide, silicon oxide, the amorphous silicon aluminium, and clay is that kaolin is or/and halloysite.

Reaction conditions is as follows: 150～350 ℃ of temperature, preferred 1～the 900kPa of pressure 1～1000kPa (all pressure of the present invention are gauge pressure), the weight ratio of catalyzer and alcohols feedstock is 0.001～50 preferred 0.005～40, reaction times 0.1-20 second, preferred 0.5-10 second.

Participate in the 0.1-100% that empyreumatic part accounts for the carbon deposited catalyst gross weight in the carbon deposited catalyst.The partial product Pd/carbon catalyst enters revivifier to carry out under the situation of coke burning regeneration, remaining carbon deposited catalyst Returning reactor, and described partial product Pd/carbon catalyst accounts for the 0.1-99% of carbon deposited catalyst gross weight.

Described single hop regeneration or the two-stage regeneration of being regenerated as, described regenerated catalyst is that partial regeneration catalyzer (i.e. half regenerated catalyst) is or/and the holomorphosis catalyzer.

The catalyzer of the described Y of containing series zeolite is selected from one or more the mixture in fresh catalyzer, regenerated catalyst, half regenerated catalyst, the carbon deposited catalyst.

In the method for the invention, methyl alcohol generation dehydration reaction, reaction product obtains gaseous product based on dme through separation, can directly be used as fuel such as civil liquefied gas etc.Gaseous product also can obtain highly purified dme by further separating, and is used as fine chemicals.The liquid product that separation obtains returns the Dehydration of methanol device and reacts.

The method from the methanol production dme that adopts the present invention to propose can effectively be controlled the bed temperature of reaction, guarantees that methyl alcohol is converted into dme continuously.Methanol conversion is generally more than 80% among the present invention, and the selectivity of dme is more than 98%, and under optimum condition, methanol conversion is generally more than 85%, and the selectivity of dme is more than 98%.

Description of drawings

Fig. 1 is one of method flow synoptic diagram of producing dimethyl ether by fluidized catalytic gas-phase dehydration of methanol.

Fig. 2 is the embodiment synoptic diagram that adopts circulation behind heat-obtaining, the carbon deposited catalyst stripping in the reactor bed, the interior heat-obtaining of regenerated catalyst.

Fig. 3 is the embodiment synoptic diagram that adopts heat-obtaining, regenerated catalyst outside heat removing in the reactor bed.

Fig. 4-6 adopts heat-obtaining, carbon deposited catalyst round-robin embodiment synoptic diagram in the reactor bed.

Fig. 7 is the metacyclic embodiment synoptic diagram of carbon deposited catalyst outside heat removing behind the employing stripping.

Fig. 8 adopts heat-obtaining, not steam stripped carbon deposited catalyst round-robin embodiment synoptic diagram in the reactor bed.

Embodiment

Be further described below in conjunction with the method for accompanying drawing, but therefore do not limit the present invention producing dimethyl ether by fluidized catalytic gas-phase dehydration of methanol provided by the present invention.Fig. 1 to Fig. 8 provides catalyzer heat-obtaining mode and catalyst recirculation mode different in the fluidized catalytic reaction regenerative process of dimethyl ether by methanol dehydration.

1 is the fluidized-bed layer reactor of methanol dehydration in Fig. 1～8, and 2 is catalyst regenerator, and 3 is stripper, and 4,9 is cyclonic separator, and 5 is the gas collection chamber, and 6 is the riser reactor of methanol dehydration, and 7,8 is heat collector, and other label is all represented pipeline.

Fig. 1 is one of method flow synoptic diagram of producing dimethyl ether by fluidized catalytic gas-phase dehydration of methanol.The used device of method of the producing dimethyl ether by fluidized catalytic gas-phase dehydration of methanol that the present invention proposes is mainly reaction-regeneration system, comprises catalyzer heat-obtaining system.Reaction-regeneration system is the major portion of dimethyl ether by methanol dehydration and catalyst regeneration, in the reaction process by adjusting the temperature of reaction and the methyl alcohol residence time with the optimal conversion that reaches methyl alcohol and the best selective of dme.Catalyst regeneration is the key of assurance device operate continuously, reacted catalyst surface generation carbon deposit, and active the reduction by activation recovering behind the catalyst regeneration, sent into reactive system again.Resultant of reaction separates by cyclonic separator with catalyzer, enters the rear portion separation and recovery system then, and catalyzer is then got back to reaction or entered regeneration system rapidly or directly enter regeneration system rapidly regeneration behind stripping.Catalyzer heat-obtaining system is mainly used to control reaction temperature, guarantees that Dehydration of methanol has high transformation efficiency and dme selectivity.

The flow process of method shown in Figure 1 is as follows:

Methanol feedstock enters riser reactor 6 through pipeline 61, carbon deposited catalyst behind the stripping enters riser reactor 6 through pipeline 32, regenerated catalyst and not steam stripped carbon deposited catalyst mix after pipeline 73 enters riser reactor 6, methanol feedstock and catalyzer are by riser reactor 6 contact reactss, simultaneously catalyzer is promoted to bed reactor 1, dehydration reaction further takes place in methyl alcohol in bed reactor.The partial product Pd/carbon catalyst is carried by reaction product and enters cyclonic separator 4.Reaction product is separated through cyclonic separator 4 and is obtained carbon deposited catalyst and product stream, and wherein the product pipeline 42 of flowing through directly is sent to collection chamber 5, and this product pipeline 51 of flowing through is drawn further separation and obtained purpose product dme; Carbon deposited catalyst solid particulate after the separation is circulated again by cyclone dip-leg 41 and turns back to fluidized-bed layer reactor 1.

Reaction obtains carbon deposited catalyst and is divided into two portions, wherein a part of carbon deposited catalyst enters heat collector 7 through pipeline 12 to be mixed with regenerated catalyst from pipeline 21, behind heat-eliminating medium such as water heat-obtaining, return riser reactor 6 through pipeline 73 circulations from pipeline 74; Another part carbon deposited catalyst removes stripper 3 by pipeline 11, and stripped vapor enters stripper 3 through pipeline 33, and the gas behind the stripping enters bed reactor 1 top by pipeline 33.Carbon deposited catalyst behind the stripping is divided into two-way again, wherein one the tunnel enter catalyst regenerator 2 through pipeline 31, containing the oxygen regeneration gas enters 2 pairs of catalyzer of revivifier through pipeline 23 and carries out coke burning regeneration from the bottom, regenerated flue gas leaves revivifier 2 through pipeline 22 from the top, regenerated catalyst enters heat collector 7 through pipeline 21 to be mixed with carbon deposited catalyst from pipeline 12, behind heat-eliminating medium such as water heat-obtaining, be circulated to riser reactor 6 bottoms and raw material contact reacts through pipeline 73 from pipeline 74; Carbon deposited catalyst behind another road stripping directly returns riser tube 6 bottoms and raw material contact reacts by stripper 3 bottoms through pipeline 32 without regeneration.

Fig. 2 compared to Figure 1, different is that Fig. 1 adopts the outside heat removing mode, catalyzer is taken heat away when the reactor outer loop.What Fig. 2 mainly adopted is interior heat-obtaining mode, and heat-obtaining pipeline 11 places bed reactor 1 inside, and the heat that reaction produces is taken away, keeps suitable bed temperature of reaction.The catalyst recirculation mode is also different with Fig. 1 among Fig. 2, and regenerated catalyst, the carbon deposited catalyst from

pipeline

23,12 enters stripper 3 mixing strippings respectively.Stripper 3 links to each other with bed reactor 1, riser reactor 6 on one side, and the other side links to each other with revivifier 2.Carbon deposited catalyst is delivered to stripper 3 by the pipeline 12 of bed reactor 1 bottom, partial product Pd/carbon catalyst behind the stripping is sent into revivifier 2 coke burning regenerations by the pipeline 32 of stripper 3 bottoms again, regenerated catalyst after the recovery activity is got back to stripper 3 by pipeline 23 and is remained to circulate jointly after carbon deposited catalyst mixes and is back to riser reactor 6 through pipeline 31, with raw material continuation contact reacts.Regenerated catalyst, carbon deposited catalyst thorough mixing, stripping under assisting in the stripper 3 among the present invention from the steam of pipeline 33, recycle has not only guaranteed activity of such catalysts, and has reduced the quantity of regenerated catalyst, alleviated the load of revivifier, the revivifier scale down.The regeneration of catalyzer application of air, the regenerated flue gas emptying of generation is handled.For the purpose of simplify describing, herein and hereinafter, the part identical with last width of cloth figure described all and omitted, but this does not influence those of ordinary skills' the understanding of the present invention.

The dual mode of the interior outside heat removing of reactor possesses simultaneously among Fig. 3, but the relative Fig. 1 of the Recycle design of catalyzer, Fig. 2 are simple.The part catalyzer is directly sent into revivifier 2 regeneration at bed reactor 1 by pipeline 12, and the catalyzer after the regeneration enters heat collector 8 by pipeline 23 heat is taken away, and the regenerated catalyst after the cooling turns back to riser reactor 6 and raw material contact reacts through pipeline 81.Loosening steam is sent into from heat collector 9 bottoms by pipeline 83, enters revivifier 2 tops by pipeline 82 again, is then discharged by pipeline 22 with regenerated flue gas.The conversion of raw material and product selectivity are very responsive for temperature.It is thermopositive reaction that methanol gas phase dehydration generates dme, in order to keep the temperature of bed reactor 1, need in reaction process unnecessary heat be taken away, therefore inserts heat-obtaining pipeline 11 in bed reactor 1 inside.Water vapor or other medium can be walked in heat removing tube inside.Because regenerated catalyst temperature is higher, regenerated catalyst is recirculated directly back to riser reactor 6 can make temperature of reaction raise, be unfavorable for reaction, therefore adopted the outside heat removing mode of regenerated catalyst circulation time simultaneously, the regenerated catalyst heat collector is installed before regenerated catalyst returns reactor.This interior outside heat removing mode of regenerated catalyst has guaranteed the constant of temperature of reaction, the recycling of heat and the selectivity of dme effectively.

What Fig. 4 adopted is interior heat-obtaining mode, and the partial product Pd/carbon catalyst direct cycles to the bottom of riser reactor 6 through pipeline 13, and the partial product Pd/carbon catalyst is circulated to revivifier 2 and regenerates, and regenerated catalyst is circulated to the bottom of riser reactor 6 through pipeline 23.Circulating simultaneously by two-way to alleviate revivifier load, guarantees catalyst activity and reserve, keeps the heat balance of system simultaneously.Pre-lift gas enters riser reactor 6 through pipeline 62 from the bottom, the carbon deposited catalyst from pipeline 13 is promoted.

The Recycle design of the heat-obtaining mode of Fig. 5 and Fig. 4 and regenerated catalyst, carbon deposited catalyst is all identical.Unique difference is that the entry position when regenerated catalyst cycles back to riser tube with carbon deposited catalyst is different.The inlet of carbon deposited catalyst shown in Figure 4 is in the regenerated catalyst bottom that enters the mouth.That is to say that raw material, contacts in the carbon deposited catalyst ingress with the carbon deposited catalyst that returns riser tube 6 earlier from the bottom to top in the course of conveying at riser tube 6.When raw material and carbon deposited catalyst together are promoted to the regenerated catalyst ingress, the regenerated catalyst that returns from revivifier 2 again with carbon deposited catalyst and raw material contact reacts together, be promoted to bed reactor 1 jointly.And among Fig. 5, it is identical that the entry position of riser tube 6 is returned in the circulation of regenerated catalyst and carbon deposited catalyst, is equivalent to the two-way catalyzer and contacts, react, promote with raw material again after mix earlier the riser tube bottom.

Bed reactor 1 vertical cyclonic separator shown in Figure 6 is two-stage series also.The mixture flow of reacting product stream and carbon deposited catalyst is delivered to cyclonic separator 4 from bed reactor 1 top and is carried out flash trapping stage, and the catalyst solid particle after separating returns bed reactor 1 bottom through pipeline 41 circulations; Being mingled with incomplete on a small quantity isolating catalyst solid particle reaction product enters cyclonic separator 9 through pipeline 42 and carries out secondary and separate.The separating obtained pure reaction product pipeline 92 of flowing through enters collection chamber 5 and collects, and solid catalyst particle returns bed reactor 1 bottom through pipeline 91 circulations.

Material benzenemethanol needed the preheating vaporization process before entering riser reactor, this part heat can be from catalyst stripping or regenerative process, as shown in Figure 7.Catalyzer is sent into revivifier 2 or stripper 3 in bed reactor 1 bottom, because reaction process is thermopositive reaction, the heat that catalyzer has in regeneration and stripping process is very high relatively, as if being returned by catalyst recirculation, this part heat brings reactor into, the rising of temperature of reaction be can cause, the conversion of methyl alcohol and the generation of dme are unfavorable for.Heat collector 7 internal pipelines 61 are walked the cold methanol raw material, not only can utilize the heat of catalyzer to make feed vaporization, have reduced the catalyzer self heat again.Heat energy is reused, and has improved economic benefit for refinery or chemical plant, kills two birds with one stone.

Fig. 8 and Fig. 1 relatively only adopt the inside heat removing mode, and do not have outside heat-obtaining.Carbon deposited catalyst by bed reactor 1 bottom input stripper 3 after, by 3 fens two-way of stripper, wherein one the tunnel through pipeline 32 directly circulation return riser reactor 6, another road enters revivifier 2 manipulation of regeneration through pipeline 31.Catalyzer after the regeneration directly enters riser reactor 6 by the regenerated catalyst inlet without heat-obtaining through pipeline 23 and participates in reaction.

The following examples will give further instruction to present method, but therefore not limit present method.

Test is to carry out on medium-sized tester, and methanol reactor is riser tube+fluidized-bed.Methanol feedstock (Beijing Chemical Plant's production) character used among the embodiment is as shown in table 1.

Embodiment 1

Used catalyzer board code name is MTD-1 (contain 30 heavy %USY zeolites, 5 weigh the %ZSM-5 zeolites, and surplus is a carrier, all is benchmark with the total catalyst weight) in the present embodiment.

The gaseous methanol raw material enters reactor and contacts with the MTD-1 catalyzer, 270 ℃ of temperature, and pressure (gauge pressure) 0.3MPa, the weight ratio of catalyzer and methanol feedstock (agent alcohol ratio) is 1.5, weight hourly space velocity 3.0h ^-1Condition under react, reactant flow obtains carbon deposited catalyst and product stream through separation, this product stream further separates and obtains purpose product dme, product distributes as shown in table 2, unreacted methanol is returned fluidized-bed reactor; Carbon deposited catalyst is divided into two portions, wherein behind the carbon deposited catalyst stripping of 50 heavy %, wherein carbon deposited catalyst goes revivifier to carry out coke burning regeneration behind the 80 heavy % strippings, carbon deposited catalyst Returning reactor behind the 20 heavy % strippings, the carbon deposited catalyst of regenerated catalyst and residue 50 heavy % enters heat collector to be mixed, and is cooled to 180 ℃ of Returning reactors (referring to Fig. 1) through outside heat removing.

Embodiment 2

Used catalyzer code name is MTD-2 (contain 35 heavy %USY zeolites, surplus is a carrier, all is benchmark with the total catalyst weight) in the present embodiment

The gaseous methanol raw material enters reactor and contacts with the MTD-2 catalyzer, 250 ℃ of temperature, and pressure (gauge pressure) 0.2MPa, the weight ratio of catalyzer and methanol feedstock (agent alcohol ratio) is 10, weight hourly space velocity 20h ^-1Condition under react, reactant flow obtains carbon deposited catalyst and product stream through separation, this product stream further separates and obtains purpose product dme, product distributes as shown in table 2, excessive methyl alcohol returns fluidized-bed reactor; Carbon deposited catalyst all goes revivifier to carry out coke burning regeneration.After whole carbon deposited catalyst regeneration, regenerated catalyst is cooled to 280 ℃ and returns fluidized bed circulation use (referring to Fig. 3).

Embodiment 3

Used catalyzer code name is MTD-3 (contain 30 heavy %USY zeolites, 5 weigh the %Beta zeolites, and surplus is a carrier, all is benchmark with the total catalyst weight) in the present embodiment.

The gaseous methanol raw material enters reactor and contacts with the MTD-3 catalyzer, 210 ℃ of temperature, and pressure (gauge pressure) 0.4MPa, the weight ratio of catalyzer and methanol feedstock (agent alcohol ratio) is 3, weight hourly space velocity 0.5h ^-1Condition under react, reactant flow obtains carbon deposited catalyst and product stream through separation, this product stream further separates and obtains purpose product dme, product distributes as shown in table 2, excessive methyl alcohol returns fluidized-bed reactor; Carbon deposited catalyst is divided into two portions, and wherein the carbon deposited catalyst of 25 heavy % goes revivifier to carry out coke burning regeneration, and riser tube is returned in the carbon deposited catalyst circulation of residue 75 heavy %.After the carbon deposited catalyst regeneration of 25 heavy %, regenerated catalyst is cooled to 250 ℃ and returns the fluidized bed circulation use, entry position when regenerated catalyst cycles back to riser tube with carbon deposited catalyst is different, and the inlet of carbon deposited catalyst is in the regenerated catalyst bottom (referring to Fig. 4) that enters the mouth.

Embodiment 4

Used catalyzer code name is MTD-4 (contain 30 heavy %USY zeolites, 5 weigh the %SAPO molecular sieves, and surplus is a carrier, all is benchmark with the total catalyst weight) in the present embodiment.

The gaseous methanol raw material enters fluidized-bed reactor and contacts with the MTD-4 catalyzer, 250 ℃ of temperature, and pressure (gauge pressure) 0.1MPa, the weight ratio of catalyzer and methanol feedstock (agent alcohol ratio) is 5, weight hourly space velocity 10h ^-1Condition under react, reactant flow obtains carbon deposited catalyst and product stream through separation, this product stream further separates and obtains purpose product dme, product distributes as shown in table 2, excessive methyl alcohol returns fluidized-bed reactor; Carbon deposited catalyst is divided into two portions, and wherein the carbon deposited catalyst of 10 heavy % goes revivifier to carry out coke burning regeneration, and riser reactor is returned in the carbon deposited catalyst circulation of residue 90 heavy %.After the carbon deposited catalyst regeneration of 10 heavy %, regenerated catalyst is cooled to 340 ℃ and returns the fluidized bed circulation use, and regenerated catalyst circulates with carbon deposited catalyst and returns the entry position identical (referring to Fig. 5) of riser tube.

Table 1

Methanol content, heavy %

≥99.5?

Density (20 ℃), g/ml	0.792?
		Molecular weight	32.04?
Boiling point	64.5?

Table 2

Embodiment	1?	2?	3?	4?
					The activity of such catalysts component	Y+ZSM-5?	Y?	Y+Beta?	Y+SAPO?
The catalyzed conversion of methyl alcohol	?	?	?	?
					Reaction conditions	?	?	?	?
Temperature, ℃	270?	250?	210?	250?
					Pressure (gauge pressure), MPa	0.3?	0.2?	0.4?	0.1?
Agent alcohol ratio	1.5?	10?	3?	5?
					Weight hourly space velocity, h ^-1	3?	20?	0.5?	10?
Product distributes, heavy %	?	?	?	?
					Dme	58.58?	57.92?	60?	59.24?
Light hydrocarbons	0.65?	0.62?	0.61?	0.63?
					Water	24.88?	24.22?	24.93?	24.72?
Coke	0.87?	0.59?	0.52?	0.57?
					Unconverted methyl alcohol	15.02?	16.66?	13.94?	14.84?
Conversion of methanol, %	84.98?	83.34?	86.06?	85.16?
					The dme selectivity, %	＞98?	＞98?	＞98?	＞98?

Claims

1. the method from the methanol production dme is characterized in that this method comprises the following steps:

A kind of method of producing dimethyl ether by fluidized catalytic gas-phase dehydration of methanol, methanol feedstock contacts in riser tube+fluidized-bed reactor with the catalyzer that contains the Y series zeolite, be 0.001～50 in the weight ratio of 150～350 ℃ of temperature, catalyzer and methanol feedstock, react under the condition of reaction times 0.1-20 second, pressure 1～1000kPa, by heat collector being set in fluidized reactor bed inside; And/or the partial product Pd/carbon catalyst comes out from fluidized-bed reactor bed top, loops back the riser tube of fluidisation reactor bed bottom through outside heat removing, and carbon deposited catalyst is through stripping or without stripping in the working cycle; And/or regenerated catalyst returns the riser tube of fluidized reactor bed bottom through outside heat removing or interior heat-obtaining, and controlling flow fluidized bed reactor bed temperature is below 350 ℃, and reactant flow obtains carbon deposited catalyst and purpose product dme through separation; The carbon deposited catalyst of separating from cyclonic separator loops back the fluidisation bed, and the carbon deposited catalyst in the fluidized-bed is partly or entirely through stripping or enter revivifier without stripping and carry out coke burning regeneration, and the regenerated catalyst Returning reactor contacts with methanol feedstock.

2. according to the method for claim 1, the content that it is characterized in that methyl alcohol in the described methanol feedstock is the heavy % of 5-100.

3. according to the method for claim 1, the content that it is characterized in that methyl alcohol in the described methanol feedstock is the heavy % of 50-100.

4. according to the method for claim 1, the content that it is characterized in that methyl alcohol in the described methanol feedstock is the heavy % of 90-100.

5. according to the method for claim 1, the catalyzer that it is characterized in that the described Y of containing series zeolite is Y series zeolite and other the optional molecular sieve that does not contain inorganic oxide and clay.

6. according to the method for claim 1, the catalyzer that it is characterized in that the described Y of containing series zeolite is to contain the Y series zeolite of inorganic oxide, clay and other optional molecular sieve.

7. according to the method for claim 5 or 6, it is characterized in that described other molecular screening one or more in mesopore zeolite, Beta zeolite, SAPO molecular sieve.

8. according to the method for claim 5 or 6, the weight ratio that it is characterized in that described other molecular sieve and Y series zeolite is 0-10.

9. according to the method for claim 1, it is characterized in that the catalyzer of the described Y of containing series zeolite comprises Y series zeolite, mesopore zeolite, inorganic oxide and clay.

10. according to claim 1,5 or 6 method, it is characterized in that described Y series zeolite is selected from one or more the mixture among Y, HY, REY, REHY, USY, the REUSY.

11., it is characterized in that described mesopore zeolite comprises ZRP series, ZSP series, ZSM series zeolite and derives or modified zeolite according to the method for claim 7.

12., it is characterized in that described mesopore zeolite comprises ZRP series, ZSP series, ZSM series zeolite and derives or modified zeolite according to the method for claim 9.

13. according to the method for claim 9, it is characterized in that the weight ratio of described mesopore zeolite and Y series molecular sieve is 0.1-10, mesopore zeolite and Y series zeolite sum account for the heavy % of 10-80 of total catalyst weight.

14. according to the method for claim 5 or 6, it is characterized in that described inorganic oxide is selected from one or more the mixture in aluminum oxide, silicon oxide, the amorphous silicon aluminium, clay is that kaolin is or/and halloysite.

15. according to the method for claim 1, it is characterized in that reaction conditions is as follows: pressure 1～900kPa, the weight ratio of catalyzer and methanol feedstock is 0.005～40, reaction times 0.5-10 second.

16., it is characterized in that participating in the described carbon deposited catalyst 0.1-100% that empyreumatic part accounts for the carbon deposited catalyst gross weight according to the method for claim 1.

17. according to the method for claim 1, it is characterized in that the partial product Pd/carbon catalyst enters revivifier and carries out under the situation of coke burning regeneration, remaining carbon deposited catalyst Returning reactor, described partial product Pd/carbon catalyst accounts for the 0.1-99% of carbon deposited catalyst gross weight.

18. according to the method for claim 1, it is characterized in that described single hop regeneration or the two-stage regeneration of being regenerated as, described regenerated catalyst is that the partial regeneration catalyzer is or/and the holomorphosis catalyzer.

19. according to the method for claim 1, the catalyzer that it is characterized in that the described Y of containing series zeolite is selected from one or more the mixture in fresh catalyzer, regenerated catalyst, half regenerated catalyst, the carbon deposited catalyst.

20., it is characterized in that heat collector being set in fluidized reactor bed inside according to the method for claim 1; Simultaneously the partial product Pd/carbon catalyst comes out from fluidized reactor bed top, loops back the riser tube of fluidisation reactor bed bottom through outside heat removing, and carbon deposited catalyst is through stripping or without stripping in the working cycle.

21., it is characterized in that heat collector being set in fluidized reactor bed inside according to the method for claim 1; Regenerated catalyst returns the riser tube of fluidized reactor bed bottom through outside heat removing or interior heat-obtaining simultaneously.

22., it is characterized in that the partial product Pd/carbon catalyst comes out from fluidized reactor bed top according to the method for claim 1, loop back the riser tube of fluidisation reactor bed bottom through outside heat removing, carbon deposited catalyst is through stripping or without stripping in the working cycle; Regenerated catalyst returns the riser tube of fluidized reactor bed bottom through outside heat removing or interior heat-obtaining simultaneously.

23., it is characterized in that heat collector being set in fluidized reactor bed inside according to the method for claim 1; Simultaneously the partial product Pd/carbon catalyst comes out from fluidized reactor bed top, loops back the riser tube of fluidisation reactor bed bottom through outside heat removing, and carbon deposited catalyst is through stripping or without stripping in the working cycle; Regenerated catalyst returns the riser tube of fluidized reactor bed bottom through outside heat removing or interior heat-obtaining simultaneously.

24., it is characterized in that the entry position when regenerated catalyst cycles back to riser tube with carbon deposited catalyst is identical according to the method for claim 1.

25. according to the method for claim 1, it is characterized in that the entry position when regenerated catalyst cycles back to riser tube with carbon deposited catalyst is different, the inlet of carbon deposited catalyst is in the regenerated catalyst bottom that enters the mouth.

26., it is characterized in that described cyclonic separator is 1 grade or 2 grades according to the method for claim 1.