CN101104575B - Method for producing dimethyl ether from methanol by combination hydrocarbons catalytic conversion - Google Patents
Method for producing dimethyl ether from methanol by combination hydrocarbons catalytic conversion Download PDFInfo
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Abstract
Disclosed is a combined hydrocarbons catforming method to produce dimethyl ether from carbinol. Carbinol raw materials contact with Y zeolite catalysts and the reaction product flow is separated to get coked catalysts and target carbinol; hydrocarbon raw materials contact with Y zeolite catalysts and the reaction product flow is separated to get spent catalysts and reaction effluent and the reaction effluent is further separated to get gas and liquid products such as gasoline; all or part of the coked catalysts or spent catalysts get into a reactivator for coke-burning regeneration; the regenerated catalysts are divided into two parts, one part returns to contact with the hydrocarbon raw materials and the other part, after cooling, returns to contact with the ethanol raw materials. The method properly uses the surplus heat energy in the course of hydrocarbons catalytic conversion, solving the problem of heat energy supply in carbinol conversion, ensuring that the carbinol can be converted to dimethyl ether continuously.
Description
Technical field
The present invention relates to a kind of method, more particularly, the invention belongs to a kind of method of producing dimethyl ether from methanol by combination hydrocarbons catalytic conversion 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 2-25W%, 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 of methyl alcohol need be finished at a certain temperature, though coking phenomenon is arranged in the reaction process, amount of coke is not enough to keep the heat balance of technological process.
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 from methanol by combination hydrocarbons catalytic conversion.
The method of producing dimethyl ether from methanol by combination hydrocarbons catalytic conversion provided by the invention comprises the following steps:
(1), methanol feedstock contacts with the catalyzer that contains the Y series zeolite, reactant flow obtains carbon deposited catalyst and purpose product dme through separation;
(2), hydrocarbon raw material contacts with the catalyzer that contains the Y series zeolite, reactant flow obtains reclaimable catalyst and reaction oil gas through separation, oil gas further separates and obtains products such as gas, gasoline;
(3), the carbon deposited catalyst of step (1) all or part of revivifier that enters of reclaimable catalyst part or all of, step (2) carries out coke burning regeneration, regenerated catalyst is divided into two portions, wherein a part is returned step (2), returns step (1) after another part cooling.
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 the laggard promoting the circulation of qi of reaction product heat exchange charging mutually.
Described hydrocarbon raw material is selected from C
4 +The mixture of one or more in hydro carbons, crude oil, gasoline, diesel oil, vacuum gas oil, coker gas oil, deasphalted oil, hydrogenation tail oil, long residuum, the vacuum residuum, the mixture of one or more in preferred vacuum gas oil, coker gas oil, deasphalted oil, hydrogenation tail oil, long residuum, the vacuum residuum.
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 inorganic oxide, clay, Y series zeolite, optional other 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.
The reaction conditions of step (1) is as follows: 100～550 ℃ preferred 150～380 ℃ of temperature, preferred 1～the 500kPa of pressure 1～1000kPa (all pressure of the present invention are gauge pressure), the weight ratio of catalyzer and methanol feedstock is 0.001～50 preferred 0.005～40, weight hourly space velocity 0.01～100h
-1Preferred 0.1～50h
-1
The reaction conditions of step (2) is as follows: 400～700 ℃ of temperature, and pressure 1～1000kPa, the weight ratio of catalyzer and hydrocarbon raw material is 1～30, time 1～10s.
The catalytic conversion process of step (2) comprises conventional catalytic cracking process and various families Technology thereof such as DCC technology, CPP technology, MIP technology, MIP-CGP technology, MGD technology, MGG technology, ARGG technology, SHMP technology etc.
Participate in the 0.5-100% that empyreumatic part accounts for the carbon deposited catalyst gross weight in the carbon deposited catalyst of step (1).Carry out under the situation of coke burning regeneration when the partial product Pd/carbon catalyst of step (1) enters revivifier, remaining carbon deposited catalyst returns step (1) or/and step (2), and described partial product Pd/carbon catalyst accounts for the 0.5-99% of carbon deposited catalyst gross weight.
Participating in 1-100%. that empyreumatic part accounts for the reclaimable catalyst gross weight in the reclaimable catalyst of step (2) carries out under the situation of coke burning regeneration when the part reclaimable catalyst of step (2) enters revivifier, remaining reclaimable catalyst returns step (1), and described part reclaimable catalyst accounts for the 1-99%. of reclaimable catalyst gross weight
Described single hop regeneration or the two-stage regeneration of being regenerated as of step (3), 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 the containing series zeolite of step (1) is selected from one or more the mixture in the reclaimable catalyst of half regenerated catalyst, step (2) of regenerated catalyst, the step (3) of fresh catalyzer, step (3).
Step (1), the used reactor of step (2) is movably reactor of catalyzer, be selected from fluidized-bed, riser tube, downstriker transfer limes reactor, moving-bed, the compound reactor that constitutes by riser tube and fluidized-bed, the compound reactor that constitutes by riser tube and downstriker transfer limes, the compound reactor that constitutes by two or more riser tubes, the compound reactor that constitutes by two or more fluidized-beds, the compound reactor that constitutes by two or more downstriker transfer limess, by the compound reactor that two or more moving-beds constitute, above-mentioned every kind of reactor can be divided into two or more reaction zones.The preferred reactor of step (1) is a more preferably dense phase fluidized bed of fluidized-bed; The preferred reactor of step (2) is a riser tube.Described riser tube be selected from the equal diameter riser tube, etc. in linear speed riser tube, the various change diameter riser tube one or more.That described fluidized-bed is selected from is fixed fluidized bed, in the dispersion fluidized bed, bubbling bed, turbulent bed, fast bed, conveying bed, dense phase fluidized bed one or more.
Above-mentioned reactor can use existing catalyst cracker, also can carry out necessary transformation to existing catalyst cracker, can also use and the similar reactor of existing catalyst cracker 26S Proteasome Structure and Function.
The regenerated catalyst that returns step (1) reactor is earlier through being cooled to 100～650 ℃.Can adopt direct or indirect heat exchange mode cooling.The direct heat exchange mode is exactly with temperature lower air and the direct contact heat-exchanging of regenerated catalyst.This strand air is to be sent to all or part of of revivifier air through air compressor machine compression, promptly utilizes the high temperature heat preheating of partial regeneration agent to enter the air of revivifier.The direct heat exchanger form is fluidized-bed or riser tube, through the isolating catalyzer that is cooled of cyclonic separator through the laggard methyl alcohol catalytic conversion reactor of superheated vapour stripping foreign gas (nitrogen, oxygen, carbonic acid gas etc.); The indirect heat exchange mode is used indirect heat exchanger exactly, and the catalyzer of heat passes through from tube side, and water vapor is walked shell side.
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, also can deliver to catalytic cracking unit and further use.
Adopt the method for the associating catalyzed conversion of the present invention's proposition, both rationally used the superfluous heat energy of hydro carbons catalyzed conversion, solved the heat supply problem of methanol conversion again, guarantee that methyl alcohol is converted into dme continuously from the methanol production dme.Methanol conversion is generally more than 75% among the present invention, and the selectivity of dme is more than 98%, and under optimum condition, methanol conversion is generally more than 80%, and the selectivity of dme is more than 99%.
Of the present invention and the resulting carbon deposited catalyst of Dehydration of methanol process also can the Returning catalyticing cracking device revivifier, catalyzer through regeneration after, can reuse, the production of catalytic cracking unit and product are distributed does not have disadvantageous effect.
Of the present invention and the resulting carbon deposited catalyst Returning catalyticing cracking device of Dehydration of methanol process reactor, reuse, the production of catalytic cracking unit and product are distributed does not have disadvantageous effect yet.
Description of drawings
Fig. 1 is the methodological principle schematic flow sheet of producing dimethyl ether from methanol by combination hydrocarbons catalytic conversion provided by the invention.
Fig. 2 is the method preferred flow synoptic diagram of producing dimethyl ether from methanol by combination hydrocarbons catalytic conversion provided by the invention.
Embodiment
Below in conjunction with accompanying drawing method provided by the present invention is further detailed, but does not therefore limit the present invention.
Fig. 1 is the methodological principle schematic flow sheet of producing dimethyl ether from methanol by combination hydrocarbons catalytic conversion provided by the invention.Wherein reactor 2 is selected from fluidized-bed, riser tube, downstriker transfer limes reactor, moving-bed, the compound reactor that constitutes by riser tube and fluidized-bed, the compound reactor that constitutes by riser tube and downstriker transfer limes, the compound reactor that constitutes by two or more riser tubes, the compound reactor that constitutes by two or more fluidized-beds, the compound reactor that constitutes by two or more downstriker transfer limess, by the compound reactor that two or more moving-beds constitute, above-mentioned every kind of reactor can be divided into two or more reaction zones.
Methanol feedstock from pipeline 1 enters reactor 2, contacts with the catalyzer that contains the Y series zeolite from pipeline 14, and 100～550 ℃ of temperature, pressure 1～1000kPa, the weight ratio of catalyzer and methanol feedstock is 0.001～50, weight hourly space velocity 0.01～100h
-1Condition under react, reactant flow obtains carbon deposited catalyst and product stream through separation, this product pipeline 3 of flowing through is drawn further separation and is obtained purpose product dme, superfluous methanol feedstock recycles (not marking among the figure), carbon deposited catalyst then can partly or entirely go revivifier 5 to carry out coke burning regeneration through pipeline 4, the partial product Pd/carbon catalyst can be successively through pipeline 15,14 Returning reactors 2, also can be successively through pipeline 17,10 Returning reactors 7.
Hydrocarbon raw material from pipeline 6 enters reactor 7, contact with the regenerated catalyst that contains the Y series zeolite from pipeline 10,400～700 ℃ of temperature, pressure 1～1000kPa, the weight ratio of catalyzer and hydrocarbon raw material is 1～30, react under the condition of time 1～10s, reactant flow obtains reclaimable catalyst and reaction oil gas through separation, wherein reaction oil gas is drawn further separation through pipeline 8 and is obtained gas, gasoline, products such as diesel oil (not marking among the figure), behind the reclaimable catalyst stripping, all or part ofly enter revivifier 5 through pipeline 9 and carry out coke burning regeneration, the part reclaimable catalyst can be successively through pipeline 16,14 Returning reactors 2.
Regenerated catalyst behind revivifier 5 coke burning regenerations is divided into two portions, and wherein a part is through pipeline 10 Returning reactors 7, and another part is successively after pipeline 12 enters interchanger 13 coolings, again through pipeline 14 Returning reactors 2.
Fig. 2 is the method preferred flow synoptic diagram of producing dimethyl ether from methanol by combination hydrocarbons catalytic conversion provided by the invention.
18 (comprise reactor for catalytic cracking unit among Fig. 2, revivifier, settling vessel, equipment such as stripper, do not mark among the figure), 2 are the Dehydration of methanol device. in the present invention, near catalytic cracking unit, newly add a Dehydration of methanol device 2, thermocatalyst from catalytic cracking unit 18 enters reactor 2 by pipeline 12, this thermocatalyst is selected from the regenerated catalyst of catalytic cracking unit, reclaimable catalyst, half regenerated catalyst, the mixture of one or more in the fresh catalyzer. thermocatalyst is before entering reactor 2 through pipeline 14, in heat-exchange equipment 13, cool off, methyl alcohol enters reactor 2 by pipeline 1, come in contact with thermocatalyst from pipeline 14, methyl alcohol generation dehydration reaction, after reaction finishes, generation is based on the reaction product and the catalyst separating of dme, leave reactor 2 from pipeline 19, enter separating device 20, further be divided into the dme is the gaseous product of main ingredient, and based on the liquid product of water. gaseous product is by pipeline 21 separating devices, be sent to the tank field. separate the liquid product obtain and enter catalytic cracking unit 18 by pipeline 22 and further utilizes. the catalyzer that separation obtains enters catalytic cracking unit 18 by pipeline 4 Returning catalyticing cracking devices 1. from the hydrocarbon raw material of pipeline 6, and reaction oil gas is drawn further separation through pipeline 8 and obtained gas, gasoline, products such as diesel oil (not marking among the figure).
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 wherein methanol reactor is a fluidized-bed, and the hydrocarbon reaction device is a riser tube.
The purity of methyl alcohol is 99.5 heavy % in the methanol feedstock, and hydrocarbon raw material is vacuum gas oil (VGO), and its character is as shown in table 1.Used catalyzer 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 fluidized-bed reactor and contacts with the MTD-1 catalyzer, 280 ℃ of temperature, and pressure (gauge pressure) 0.1MPa, the weight ratio of catalyzer and methanol feedstock (agent alcohol ratio) is 2.5, 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, excessive methyl alcohol returns fluidized-bed reactor; Carbon deposited catalyst is divided into two portions, and wherein the carbon deposited catalyst of 50 heavy % goes revivifier to carry out coke burning regeneration, and the carbon deposited catalyst internal recycle of residue 50 heavy % returns fluidized-bed reactor.
VGO after the preheating is after steam atomizing in the injecting lift pipe reactor, the weight ratio of steam and mixing raw material oil is 0.05: 1, mixing raw material oil contacts with the regenerated catalyst of heat in riser tube and reacts, temperature of reaction is 500 ℃, pressure (gauge pressure) 0.1MPa, the weight ratio of catalyzer and mixing raw material oil (agent-oil ratio) is 6, reaction times is 3 seconds, after reaction oil gas and mixture of catalysts go upward to the riser tube exit along riser tube, reaction product isolated and reclaimable catalyst, reaction product is introduced in the subsequent separation system after introducing settling vessel again, further is separated into various products, and product distributes as shown in table 2; And reclaimable catalyst enters stripper under the effect of gravity, sends into coke burning regeneration in the revivifier behind the water vapor stripping.
After the carbon deposited catalyst of 50 heavy % and the regeneration of whole reclaimable catalysts, be divided into two portions, wherein 690 of 90 heavy % ℃ of regenerated catalysts return riser tube and recycle, and the regenerated catalyst of remaining 10 heavy % is cooled to 180 ℃ through the water indirect heat exchange and returns fluidized bed circulation and use.
Test-results shows, after the catalyzed conversion of methyl alcohol and the associating of the catalyzed conversion of hydro carbons, can keep the thermal equilibrium of the two, does not need extra fuel or other thermal source.
The purity of methyl alcohol is 90.0 heavy % in the methanol feedstock, and hydrocarbon raw material is VGO, and its character is as shown in table 1.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 liquid methanol raw material enters fluidized-bed reactor and contacts with the MTD-2 catalyzer, 380 ℃ of temperature, and pressure (gauge pressure) 0.1MPa, the weight ratio of catalyzer and methanol feedstock (agent alcohol ratio) is 40, weight hourly space velocity 50h
-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.
VGO after the preheating is after steam atomizing in the injecting lift pipe reactor, the weight ratio of steam and mixing raw material oil is 0.05: 1, mixing raw material oil contacts with the regenerated catalyst of heat in riser tube and reacts, temperature of reaction is 500 ℃, pressure (gauge pressure) 0.1MPa, the weight ratio of catalyzer and mixing raw material oil (agent-oil ratio) is 6, reaction times is 3 seconds, after reaction oil gas and mixture of catalysts go upward to the riser tube exit along riser tube, reaction product isolated and reclaimable catalyst, reaction product is introduced in the subsequent separation system after introducing settling vessel again, further is separated into various products, and product distributes as shown in table 2; And reclaimable catalyst enters stripper under the effect of gravity, sends into coke burning regeneration in the revivifier behind the water vapor stripping.
After whole carbon deposited catalysts and whole reclaimable catalysts are regenerated together, be divided into two portions, wherein 690 of 90 heavy % ℃ of regenerated catalysts return riser tube and recycle, and the regenerated catalyst of remaining 10 heavy % is cooled to 410 ℃ through the water indirect heat exchange and returns fluidized bed circulation and use.
Test-results shows, after the catalyzed conversion of methyl alcohol and the associating of the catalyzed conversion of hydro carbons, can keep the thermal equilibrium of the two, does not need extra fuel or other thermal source.
The purity of methyl alcohol is 95.0 heavy % in the methanol feedstock, and hydrocarbon raw material is VGO, and its character is as shown in table 1.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 liquid methanol raw material enters fluidized-bed reactor and contacts with the MTD-3 catalyzer, 150 ℃ of temperature, and pressure (gauge pressure) 0.1MPa, the weight ratio of catalyzer and methanol feedstock (agent alcohol ratio) is 6, weight hourly space velocity 0.1h
-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 the carbon deposited catalyst internal recycle of residue 75 heavy % returns fluidized-bed reactor.
VGO after the preheating is after steam atomizing in the injecting lift pipe reactor, the weight ratio of steam and mixing raw material oil is 0.05: 1, mixing raw material oil contacts with the regenerated catalyst of heat in riser tube and reacts, temperature of reaction is 500 ℃, pressure (gauge pressure) 0.1MPa, the weight ratio of catalyzer and mixing raw material oil (agent-oil ratio) is 6, reaction times is 3 seconds, after reaction oil gas and mixture of catalysts go upward to the riser tube exit along riser tube, reaction product isolated and reclaimable catalyst, reaction product is introduced in the subsequent separation system after introducing settling vessel again, further is separated into various products, and product distributes as shown in table 2; And reclaimable catalyst enters stripper under the effect of gravity, sends into coke burning regeneration in the revivifier behind the water vapor stripping.
After the carbon deposited catalyst of 25 heavy % and whole reclaimable catalysts are regenerated together, be divided into two portions, wherein 690 of 90 heavy % ℃ of regenerated catalysts return riser tube and recycle, and the regenerated catalyst of remaining 10 heavy % directly is cooled to 580 ℃ through air and returns fluidized bed circulation and use.
Test-results shows, after the catalyzed conversion of methyl alcohol and the associating of the catalyzed conversion of hydro carbons, can keep the thermal equilibrium of the two, does not need extra fuel or other thermal source.
The purity of methyl alcohol is 80.0 heavy % in the methanol feedstock, and hydrocarbon raw material is the long residuum that VGO mixes 30 heavy %, and the character of long residuum is as shown in table 1.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 liquid 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 20, weighs space-time 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 50 heavy % goes revivifier to carry out coke burning regeneration, and the carbon deposited catalyst internal recycle of residue 50 heavy % returns fluidized-bed reactor.
VGO after the preheating is after steam atomizing in the injecting lift pipe reactor, the weight ratio of steam and mixing raw material oil is 0.05: 1, mixing raw material oil contacts with the regenerated catalyst of heat in riser tube and reacts, temperature of reaction is 500 ℃, pressure (gauge pressure) 0.1MPa, the weight ratio of catalyzer and mixing raw material oil (agent-oil ratio) is 6, reaction times is 3 seconds, after reaction oil gas and mixture of catalysts go upward to the riser tube exit along riser tube, reaction product isolated and reclaimable catalyst, reaction product is introduced in the subsequent separation system after introducing settling vessel again, further is separated into various products, and product distributes as shown in table 2; And reclaimable catalyst enters stripper under the effect of gravity, is divided into two portions behind the water vapor stripping, and wherein the reclaimable catalyst of 90 heavy % goes revivifier to carry out coke burning regeneration, and the reclaimable catalyst that remains 10 heavy % is cooled to 340 ℃ and is circulated to fluidized-bed reactor.
After the carbon deposited catalyst of the reclaimable catalyst of 90 heavy % and 50 heavy % is regenerated together, be divided into two portions, wherein 690 of 95 heavy % ℃ of regenerated catalysts return riser tube and recycle, and the regenerated catalyst of remaining 5 heavy % is cooled to 340 ℃ through the water indirect heat exchange and returns fluidized bed circulation and use.
Test-results shows, after the catalyzed conversion of methyl alcohol and the associating of the catalyzed conversion of hydro carbons, can keep the thermal equilibrium of the two, does not need extra fuel or other thermal source.
Table 1
| Feedstock property | VGO | Long residuum |
| Density (20 ℃), g/cm 3 | 0.9071 | 0.9387 |
| Sulphur content, ppm | 7800 | 12000 |
| Nitrogen content, ppm | 600 | 647 |
| Carbon residue, m% | 0.1 | 9.2 |
| C，m％ | 86.43 | 87.05 |
| H，m％ | 12.48 | 11.83 |
| Kinematic viscosity, mm 2/s | ||
| 80℃ | 21.28 | 325.1 |
| 100℃ | 11.32 | 129.5 |
| Condensation point, ℃ | 35 | 45 |
| True boiling point, ℃ | ＞350 | ＞450 |
| Vanadium, ppm | 0.3 | 1.7 |
| Nickel, ppm | 4.2 | 30 |
Table 2
| |
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, ℃ | 280 | 380 | 150 | 250 |
| Pressure (gauge pressure), MPa | 0.1 | 0.1 | 0.1 | 0.1 |
| Agent alcohol ratio | 2.5 | 40 | 6 | 20 |
| Weight hourly space velocity, h -1 | 3.0 | 50 | 0.1 | 10 |
| Product distributes, m% | ||||
| Dme | 53.92 | 54.73 | 54.32 | 54.67 |
| Light hydrocarbons | 0.94 | 0.95 | 0.78 | 0.82 |
| Water | 22.31 | 22.64 | 22.26 | 22.44 |
| Coke | 1.13 | 1.08 | 0.98 | 1.05 |
| Unconverted methyl alcohol | 21.7 | 20.60 | 21.66 | 21.02 |
| Conversion of methanol, % | 78.3 | 79.40 | 78.34 | 78.98 |
| The dme selectivity, % | ＞98 | ＞98 | ＞98 | ＞98 |
| The catalyzed conversion of hydro carbons | ||||
| Reaction conditions | ||||
| Temperature, ℃ | 500 | 500 | 500 | 500 |
| Pressure (gauge pressure), MPa | 0.1 | 0.1 | 0.1 | 0.1 |
| |
1 | 2 | 3 | 4 |
| Agent- |
6 | 6 | 6 | 6 |
| Time, |
3 | 3 | 3 | 3 |
| Product distributes, heavy % | ||||
| Dry gas | 3.17 | 2.78 | 2.81 | 3.14 |
| Liquefied gas | 18.04 | 17.98 | 18.21 | 18.09 |
| Gasoline | 48.26 | 48.39 | 48.01 | 47.98 |
| Diesel oil | 18.73 | 18.73 | 18.79 | 18.89 |
| Heavy oil | 4.56 | 4.64 | 4.71 | 4.78 |
| Coke | 7.24 | 7.48 | 7.47 | 7.12 |
Claims (29)
1. the method for a producing dimethyl ether from methanol by combination hydrocarbons catalytic conversion is characterized in that this method comprises the following steps:
(1), methanol feedstock contacts with the catalyzer that contains the Y series zeolite, reactant flow obtains carbon deposited catalyst and purpose product dme through separation;
(2), hydrocarbon raw material contacts with the catalyzer that contains the Y series zeolite, reactant flow obtains reclaimable catalyst and reaction oil gas through separation, oil gas further separates;
(3), the carbon deposited catalyst of step (1) all or part of revivifier that enters of reclaimable catalyst part or all of, step (2) carries out coke burning regeneration, regenerated catalyst is divided into two portions, wherein a part is returned step (2), returns step (1) after another part cooling.
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, it is characterized in that described hydrocarbon raw material is selected from C
4 +The mixture of one or more in hydro carbons, crude oil, gasoline, diesel oil, vacuum gas oil, coker gas oil, deasphalted oil, hydrogenation tail oil, long residuum, the vacuum residuum.
6. according to the method for claim 1, it is characterized in that described hydrocarbon raw material is selected from one or more the mixture in vacuum gas oil, coker gas oil, deasphalted oil, hydrogenation tail oil, long residuum, the vacuum residuum.
7. according to the method for claim 1, the catalyzer that it is characterized in that the described Y of containing series zeolite is the Y series zeolite, or the mixture of Y series zeolite and other molecular sieve, does not all conform to inorganic oxide and clay.
8. according to the method for claim 1, it is characterized in that the catalyzer of the described Y of containing series zeolite comprises inorganic oxide, clay, Y series zeolite and other optional molecular sieve.
9. according to the method for claim 7 or 8, it is characterized in that described other molecular screening one or more in mesopore zeolite, Beta zeolite, SAPO molecular sieve, wherein said mesopore zeolite is selected from ZRP series, ZSP series, ZSM series zeolite and modified zeolite thereof.
10. according to the method for claim 7 or 8, the weight ratio that it is characterized in that described other molecular sieve and Y series zeolite is 0-10.
11. method according to claim 1, the catalyzer that it is characterized in that the described Y of containing series zeolite comprises Y series zeolite, mesopore zeolite, inorganic oxide and clay, and wherein said mesopore zeolite is selected from ZRP series, ZSP series, ZSM series zeolite and modified zeolite thereof.
12., 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 according to claim 1,7 or 8 method.
13. according to the method for claim 11, 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 7 or 8, 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 a kaolin.
15., it is characterized in that described kaolin is halloysite according to the method for claim 14.
16., it is characterized in that the reaction conditions of step (1) is as follows according to the method for claim 1: 100～550 ℃ of temperature, gauge pressure 0～1000kPa, the weight ratio of catalyzer and methanol feedstock is 0.001～50, weight hourly space velocity 0.01～100h
-1
17., it is characterized in that the reaction conditions of step (1) is as follows according to the method for claim 1: 150～380 ℃ of temperature, gauge pressure 0～500kPa, the weight ratio of catalyzer and methanol feedstock is 0.005～40, weight hourly space velocity 0.1～50h
-1
18., it is characterized in that the reaction conditions of step (2) is as follows according to the method for claim 1: 400～700 ℃ of temperature, gauge pressure 0～500kPa, the weight ratio of catalyzer and hydrocarbon raw material is 1～30, time 1～10s.
19., it is characterized in that participating in the carbon deposited catalyst of step (1) 0.5-100% that empyreumatic part accounts for the carbon deposited catalyst gross weight according to the method for claim 1.
20. method according to claim 1 or 19, it is characterized in that partial product Pd/carbon catalyst when step (1) enters revivifier and carries out under the situation of coke burning regeneration, remaining carbon deposited catalyst returns step (1) or/and step (2), and described partial product Pd/carbon catalyst accounts for the 0.5-99% of carbon deposited catalyst gross weight.
21., it is characterized in that participating in the reclaimable catalyst of step (2) 1-100% that empyreumatic part accounts for the reclaimable catalyst gross weight according to the method for claim 1.
22. method according to claim 1 or 21, it is characterized in that part reclaimable catalyst when step (2) enters revivifier and carries out under the situation of coke burning regeneration, remaining reclaimable catalyst returns step (1), and described part reclaimable catalyst accounts for the 1-99% of reclaimable catalyst gross weight.
23. 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 of step (3), described regenerated catalyst is that the partial regeneration catalyzer is or/and the holomorphosis catalyzer.
24. method according to claim 1, it is characterized in that step (1), the used reactor of step (2) is movably reactor of catalyzer, be selected from fluidized-bed, riser tube, downstriker transfer limes reactor, moving-bed, the compound reactor that constitutes by riser tube and fluidized-bed, the compound reactor that constitutes by riser tube and downstriker transfer limes, the compound reactor that constitutes by two or more riser tubes, the compound reactor that constitutes by two or more fluidized-beds, the compound reactor that constitutes by two or more downstriker transfer limess, by the compound reactor that two or more moving-beds constitute, above-mentioned every kind of reactor can be divided into two or more reaction zones.
25. according to the method for claim 1, the reactor that it is characterized in that step (1) is a fluidized-bed; The reactor of step (2) is a riser tube.
26. according to the method for claim 24 or 25, it is characterized in that described riser tube be selected from the equal diameter riser tube, etc. in linear speed riser tube, the various change diameter riser tube one or more; That described fluidized-bed is selected from is fixed fluidized bed, in the dispersion fluidized bed, bubbling bed, turbulent bed, fast bed, conveying bed, dense phase fluidized bed one or more.
27., it is characterized in that the regenerated catalyst that returns step (1) reactor adopts direct or indirect heat exchange mode to be cooled to 100～650 ℃ earlier according to the method for claim 1.
28., it is characterized in that described direct heat exchange mode is that the direct heat exchanger form is fluidized-bed or riser tube with temperature lower air and the direct contact heat-exchanging of regenerated catalyst according to the method for claim 27; The indirect heat exchange mode is to use indirect heat exchanger, and the catalyzer of heat passes through from tube side, and water vapor is walked shell side.
29., it is characterized in that described methanol feedstock charging is liquid phase or gas phase according to the method for claim 1.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1153080A (en) * | 1995-12-29 | 1997-07-02 | 中国科学院兰州化学物理研究所 | Catalyst for direct preparation of dimethyl ether with synthetic gas |
| WO2004074228A1 (en) * | 2003-02-19 | 2004-09-02 | Sk Corporation. | Process for preparing dimethylether from methanol |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1153080A (en) * | 1995-12-29 | 1997-07-02 | 中国科学院兰州化学物理研究所 | Catalyst for direct preparation of dimethyl ether with synthetic gas |
| WO2004074228A1 (en) * | 2003-02-19 | 2004-09-02 | Sk Corporation. | Process for preparing dimethylether from methanol |
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