CN102746095A - Method for preparing petroleum-level toluene from benzene and methanol or dimethyl ether - Google Patents
Method for preparing petroleum-level toluene from benzene and methanol or dimethyl ether Download PDFInfo
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- CN102746095A CN102746095A CN2011101000043A CN201110100004A CN102746095A CN 102746095 A CN102746095 A CN 102746095A CN 2011101000043 A CN2011101000043 A CN 2011101000043A CN 201110100004 A CN201110100004 A CN 201110100004A CN 102746095 A CN102746095 A CN 102746095A
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Abstract
The invention relates to a method for preparing petroleum-level toluene from benzene and methanol or dimethyl ether, and mainly solves the problems that the production capacity of petroleum-level toluene is restricted by petroleum resources and petroleum processing capacity, benzene and methanol have excess production capacity, benzene, as a gasoline component, is strictly limited and is difficult to serve as a toluene production raw material, direct conversion of methanol or dimethyl ether into toluene has very low route selectivity and yield, as well as high material and energy consumption in existing production technologies. The method of the invention employs the following technical scheme of: using a modified solid acid catalyst, taking benzene and methanol or dimethyl ether as raw materials, under the conditions of a reaction temperature of 250-600DEG C, a reaction pressure of 0.05-5.0MPa, a raw material weight hourly space velocity of 0.3-15h<-1>, making the raw materials undergo an alkylation reaction on the catalyst so as to obtain toluene. The technical scheme of the invention well solves the problems, and can be used in the industrial production of toluene.
Description
Technical field
The present invention relates to the method for a kind of benzene and methyl alcohol or dme system grade oil toluene.
Background technology
Toluene is a kind of colourless; With the volatile liquid of special aromatising flavour, be a member of aromatic hydrocarbons, its a lot of character and benzene are very alike; In practical application, usually substituting has quite toxic benzene to use as organic solvent; Still a kind of industrial chemicals commonly used can be used for making explosive, agricultural chemicals, phenylformic acid, dyestuff, synthetic resins and terylene etc., and it also is a moity of gasoline simultaneously.
Press rule of origin, toluene can be divided into grade oil toluene and coking level toluene.Grade oil toluene mainly adopts extractive method production by CR gasoline or hydrocracking gasoline.Coking toluene is then made through fractionation by the sub product coking crude benzene of coking, and its precision is lower than the grade oil product, can only partly substitute the latter in the minority industry and use, and with respect to grade oil toluene, the shared market share of coking level toluene product can be ignored.
Grade oil toluene is for benzene, and toxicity is little, and purposes is wide, especially can be used as the raw materials for production of high-octane number component in the gasoline and YLENE and other downstream Chemicals, and consumption is very big.Because mainly from petroleum refining industry, the production capacity of toluene receives the restriction of petroleum resources and petroleum refinery capacity.
Methyl alcohol is a kind of important Organic Chemicals, and it has purposes widely in industries such as chemical industry, medicine, light industry, weavings.Increasingly mature along with the deficient day by day and coal chemical technology of world petroleum resource, the methanol production cost significantly reduces, and the methyl alcohol production capacity is rapidly expanded in recent years, has been superfluous trend, and the utilization of methyl alcohol becomes the current research focus.
With methyl alcohol is raw material, is the current main technical schemes of utilizing the methyl alcohol resource to produce toluene through aromatization system aromatic hydrocarbons technology (MTA), through laboratory study for many years, and existing at present industrial test report.
Chinese patent CN1880288 discloses a kind of process of methanol conversion for preparing arene, and this technology is raw material with methyl alcohol, is catalyzer with the modified zsm-5 zeolite, is 0.1～5.0Mpa at working pressure, and service temperature is 300～460 ℃, and the raw material liq air speed is 0.1～6.0h
-1Catalyzed conversion is for aromatic hydrocarbons being main product under the condition; Through refrigerated separation the gas-phase product lower carbon number hydrocarbons is separated with liquid product C5+ hydrocarbon; Liquid product C5+ hydrocarbon obtains aromatic hydrocarbons and non-aromatic hydrocarbons through extracting and separating.
Chinese patent CN101550051 discloses optionally technology of a kind of raising aromatization of methanol preparing aromatic hydrocarbon by converting.This technology is to be raw material with methyl alcohol; With the composite modified HZSM-5 sieve catalyst of Ga, Zn, Cu, Cr, Ag isoreactivity ion of different concns, the catalysis methanol aromizing is taked fixed bed continuous processing or floating bed continuous processing; Reaction pressure is 0.1-3.5MPa; Temperature of reaction is 380-500 ℃, and the raw material liq air speed is 0.1-10.0h-1, N
2Air speed is 120-800h
-1, arenes selectivity can reach 70%.
Yet owing to be main with benzene in the light aromatics that generates, methylbenzene selective is low, a large amount of lower carbon number hydrocarbons of by-product, heavy aromatics and coke simultaneously, and its Technological Economy property there is much controversy, and application prospect is uncertain.
Along with the ethylene industry fast development, benzene is as the main by product of naphtha cracking production ethene, and its output also significantly increases thereupon; The development of coking and steel industry also makes the output of coking benzene constantly increase; Because the increasingly stringent of global environmental protection legislation, the content of benzene will further limit in the gasoline.Can predict, superfluous relatively situation will appear in benzene yield in the long time, press for seek a kind of newly utilize approach.
The reaction of benzene and methanol alkylation generates toluene, realized that simultaneously benzene and the methanol conversion with surplus is broad-spectrum toluene, both for the chemical industry derived product provides raw material, is that aromatic hydrocarbons provides an efficient feasible new way to methanol conversion also.
Adopting benzene and methyl alcohol or dme system grade oil toluene is the new way that methyl alcohol and benzene utilize, and belongs to brand-new research field, does not see research report in this respect at present as yet.
Summary of the invention
Technical problem to be solved by this invention is that the grade oil toluene production capacity that exists in the existing production technology receives petroleum resources and refining of petroleum ability restriction, benzene and methyl alcohol over capacity, and benzene is limited and be difficult to as grade oil toluene raw materials for production as the gasoline component strictness; Methyl alcohol or dme be converted into toluene route selection property and yield low excessively; Material consumption, the problem that energy consumption is high provide a kind of new toluene working method, and it is wide that this method has raw material sources; Cost is low; Can on enterprise existing resource basis, significantly increase toluene output, and then improve the characteristics of derived product throughput, solve above-mentioned technical problem preferably.
For solving the problems of the technologies described above; The technical scheme that the present invention adopts is following: the method for a kind of benzene and methyl alcohol or dme system grade oil toluene is a raw material with benzene and methyl alcohol or dme, is 250～600 ℃ in temperature of reaction; Reaction pressure is 0.05～5.0MPa, and the raw material weight air speed is 0.3～15h
-1Under the condition, alkylated reaction takes place in raw material on solid acid catalyst, generates grade oil toluene.
In the technique scheme, said benzene benzene freezing point is greater than 5.35; Allow to contain by weight water in said methyl alcohol or the dme less than 80%; Methyl alcohol or dme content are 5～65% in the raw material beyond dewatering, and preferable range is 10～45%; Used solid acid catalyst preferred version is selected from least a in the molecular sieve of ZSM-5, ZSM-12, mordenite, USY, beta-molecular sieve, UZM molecular sieve, EU-1 molecular sieve or MCM-41; Used solid acid catalyst preferred version is selected from least a in the metallic element of Mg, Ca, Ba, Zn, Ga, Mo, Ni, Co, W, Cu, Fe, Zr, Ti, Pt, Pd, Sn, Pb, La, Ce; Used solid acid catalyst preferred version is selected from least a in the non-metallic element of P, S, Cl, B; The temperature of reaction preferable range is 300-500 ℃, and more preferably scope is 350-450 ℃; The reaction pressure preferable range is 0.1～4.0MPa, and this preferable range is 0.5～3.0MPa; Raw material weight air speed preferable range is 0.5～5.0h
-1More preferably scope is 0.8～3.0h
-1Can feed one or more in the reaction system and be selected from gases such as hydrogen, nitrogen, methane, carbon monoxide, carbonic acid gas as carrier gas, the mol ratio of benzene is less than 10.0 in carrier gas and the raw material.
Methyl alcohol and dme are good alkylating reagents; They and benzene are under the solid acid catalyst effect; Alkylated reaction can take place generate toluene and polyalkylbenzene, modification and control reaction process through to catalyzer can make methyl alcohol and benzene selective ground alkylated reaction generate toluene.
Methyl alcohol or dme with benzene generation alkylated reaction in; MTO, MTP reaction also can take place self; Generate earlier alkene, then alkene again with side reactions such as benzene generation alkylation, superimposed and MTG, thereby methylbenzene selective is reduced; Therefore, suppress the key problem in technology that these side reactions are present method.
Benzene and methyl alcohol or the reaction of dme alkylation to prepare toluene are acid catalyzed reaction; The surface acid amount and the strength of acid of catalyzer have material impact to this reaction; Weak acid and middle strong acid help the carrying out of alkylated reaction; And strong acid can cause generating side reactions increases such as alkene or MTG and toluene disproportionation, also can cause carbon distribution speed to increase simultaneously, causes rapid catalyst deactivation.
The major cause of benzene and methanol alkylation preparing methylbenzene catalyst deactivation is area carbon and molecular sieve dealuminzation, certain duration of service inner catalyst can use repeatedly through coke burning regeneration, thereby reach the purpose that prolongs catalyst life.
The present invention is a raw material with benzene and methyl alcohol; Utilize the alkylated reaction between methyl alcohol and the benzene to generate toluene, make the direct conversion aromatic hydrocarbons of methyl alcohol highly selective, widened the approach that utilizes of benzene and methyl alcohol; Solve the long-term superfluous relatively problem of benzene and methyl alcohol, further reduced raw materials cost.
The methanol conversion that the invention provides a kind of highly selective is that toluene utilizes approach, and Coal Chemical Industry, C-1 chemistry and petrochemical complex are combined, and has obtained better technical effect.
Through embodiment the present invention is done further elaboration below.
Embodiment
[embodiment 1]
Consist of 0.15%Pt-1.5%Sn-0.5%La/50%ZSM-5/50%SiO in weight
2The catalyst A effect under, be that 5.40 benzene and anhydrous methanol are raw material with freezing point, be carrier gas with hydrogen, the mol ratio of benzene is 10.0 to react in carrier gas and the raw material, reaction conditions and result see table 1:
Table 1 benzene and methyl alcohol is reaction result under the catalyst A effect
| Raw material is formed | 0.7A/0.3B | 0.8A/0.2B | 0.9A/0.1B |
| Temperature of reaction, ℃ | 400 | 350 | 300 |
| Weight space velocity, h -1 | 15.0 | 5.0 | 2.0 |
| System pressure, MPa | 0.5 | 1.5 | 2.0 |
| Liquid yield, wt% | 97.5 | 99.1 | 99.3 |
| Methylbenzene selective, mol% | 78.7 | 81.3 | 82.3 |
Annotate: A represents benzene, and B represents methyl alcohol.
Visible by table 1, adopt the present invention program, can benzene and methyl alcohol highly selective be converted into toluene.
[embodiment 2]
Consist of 5.0% phospho-wolframic acid/1.5%Ce/50%MCM-41/20% beta-molecular sieve/30%Al in weight
2O
3The catalyst B effect under, be that 5.45 benzene and moisture 50% methyl alcohol are that raw material reacts with freezing point, reaction conditions and result see table 2:
Table 2 benzene and methyl alcohol is reaction result under the catalyst B effect
| Raw material is formed | 0.3A/0.7B | 0.7A/0.3B | 0.9A/0.1B |
| Temperature of reaction, ℃ | 600 | 550 | 500 |
| Weight space velocity, h -1 | 1.5 | 0.8 | 0.3 |
| System pressure, MPa | 1.0 | 0.5 | 0.1 |
| Liquid yield, wt% | 90.2 | 96.0 | 97.4 |
| Methylbenzene selective, mol% | 63.3 | 77.1 | 79.6 |
Annotate: A represents benzene, and B represents methyl alcohol.
If when the methyl alcohol ratio was higher in the raw material, significant aromatization can take place methyl alcohol, in this patent method, methylbenzene selective is not distinguished this.
[embodiment 3]
Consist of 1.0%Zr-1.0%H in weight
2SO
4-1.0%Mo/60%USY/40%Al
2O
3Catalyzer C effect down, be that 5.40 benzene and moisture 80% methyl alcohol are that raw material reacts with freezing point, reaction conditions and result see table 3:
Table 3 benzene and methyl alcohol is reaction result under catalyzer C effect
| Raw material is formed | 0.7A/0.3B | 0.8A/0.2B | 0.9A/0.1B |
| Temperature of reaction, ℃ | 500 | 350 | 200 |
| Weight space velocity, h -1 | 10.0 | 2.5 | 0.8 |
| System pressure, MPa | 0.5 | 1.0 | 2.0 |
| Liquid yield, wt% | 98.2 | 99.5 | 99.7 |
| Methylbenzene selective, mol% | 77.0 | 79.5 | 80.5 |
Annotate: A represents benzene, and B represents methyl alcohol.
[embodiment 4]
Consist of 1.5%Mo-0.5%Ni-3.05H in weight
3PO
4/ 35%ZSM-12/35%UZM/30%Al
2O
3Catalyzer D effect down, be that 5.36 benzene and moisture 10% methyl alcohol are raw material with freezing point, be carrier gas with nitrogen, the mol ratio of benzene is 5.0 to react in carrier gas and the raw material, reaction conditions and result see table 4:
Table 4 benzene and methyl alcohol is reaction result under catalyzer D effect
| Raw material is formed | 0.5A/0.5B | 0.6A/0.4B | 0.7A/0.3B |
| Temperature of reaction, ℃ | 400 | 300 | 200 |
| Weight space velocity, h -1 | 1.5 | 0.8 | 0.2 |
| System pressure, MPa | 2.0 | 1.5 | 0.1 |
| Liquid yield, wt% | 93.7 | 96.3 | 96.5 |
| Methylbenzene selective, mol% | 74.2 | 76.1 | 79.8 |
Annotate: A represents benzene, and B is for methyl alcohol.
[embodiment 5]
Consist of 0.5%Mo-0.8%Co-3.0%Mg/50% mordenite/20% β zeolite/30%SiO in weight
2Catalyzer E effect down, be that 5.42 benzene and anhydrous methanol are raw material with freezing point, be carrier gas with methane, the mol ratio of benzene is 3.0 to react in carrier gas and the raw material, reaction conditions and result see table 5:
Table 5 benzene and methyl alcohol is reaction result under catalyzer E effect
| Raw material is formed | 0.55A/0.45B | 0.2A/0.8B |
| Temperature of reaction, ℃ | 350 | 200 |
| Weight space velocity, h -1 | 4.0 | 3.0 |
| System pressure, MPa | 2.5 | 0.1 |
| Liquid yield, wt% | 91.2 | 87.4 |
| Methylbenzene selective, mol% | 73.1 | 65.4 |
Annotate: A represents benzene, and B is for methyl alcohol.
[embodiment 6]
Consist of 2.0%Zn-1.5%Ni-0.7%Cr/60%EU-1/10%TiO in weight
2/ Al
2O
3Catalyzer F effect down, be that 5.46 benzene and anhydrous methanol are raw material with freezing point, carbon monoxide with 50% and 50% hydrogen mixed gas are carrier gas, the mol ratio of benzene is 12.0 to react in carrier gas and the raw material, reaction conditions and result see table 6:
Table 6 benzene and methyl alcohol is reaction result under catalyzer F effect
| Raw material is formed | 0.2A/0.8B | 0.5A/0.5B |
| Temperature of reaction, ℃ | 450 | 380 |
| Weight space velocity, h -1 | 5.0 | 3.0 |
| System pressure, MPa | 3.5 | 2.0 |
| Liquid yield, wt% | 88.7 | 92.1 |
| Methylbenzene selective, mol% | 66.5 | 75.6 |
Annotate: A represents benzene, and B is for methyl alcohol.
[embodiment 7]
Consist of 0.2%Pd-1.5%Pb-1.5%Fe-1.0%B/30%ZSM-5/30%USY/40%Al in weight
2O
3Catalyzer G effect down, be that 5.30 petroleum benzene and moisture 15% coal system methyl alcohol are raw material with freezing point, be carrier gas with the carbonic acid gas, the mol ratio of benzene is 3.5 to react in carrier gas and the raw material, reaction conditions and result see table 7:
Table 7 benzene and methyl alcohol is reaction result under catalyzer G effect
| Raw material is formed | 0.5A/0.5B | 0.3A/0.7B | 0.2A/0.8B |
| Temperature of reaction, ℃ | 450 | 480 | 420 |
| Weight space velocity, h -1 | 2.5 | 3.0 | 3.5 |
| System pressure, MPa | 3.0 | 4.0 | 5.0 |
| Liquid yield, wt% | 91.5 | 88.5 | 85.3 |
| Methylbenzene selective, mol% | 78.3 | 66.4 | 62.5 |
Annotate: A represents benzene, and B is for methyl alcohol.
[embodiment 8]
Consist of 2.0%Mo-3.0Cu-1.0%Ca-1.2%Cl/70%USY/30%Al in weight
2O
3Catalyzer H effect down, be that 5.42 benzene and moisture 20% methyl alcohol are that raw material reacts with freezing point, reaction conditions and result see table 8:
Table 8 benzene and methyl alcohol is reaction result under catalyzer H effect
| Raw material is formed | 0.8A/0.2B | 0.5A/0.5B | 0.7A/0.3B |
| Temperature of reaction, ℃ | 600 | 550 | 500 |
| Weight space velocity, h -1 | 2.5 | 2.0 | 1.5 |
| System pressure, MPa | 2.0 | 1.5 | 1.0 |
| Liquid yield, wt% | 98.9 | 99.3 | 99.1 |
| Methylbenzene selective, mol% | 81.3 | 78.9 | 79.1 |
Annotate: A represents benzene, and B is for methyl alcohol.
[embodiment 9]
Consist of 0.05%Pt-1.0%Ni-0.3%Ba-0.5%Ga/70%ZSM-5/30%SiO in weight
2The catalyst I effect under, be that 5.42 benzene and moisture 8% methyl alcohol are raw material with freezing point, be carrier gas with hydrogen, the mol ratio of benzene is 1.5 to react in carrier gas and the raw material, reaction conditions and result see table 9:
Table 9 benzene and methyl alcohol is reaction result under the catalyst I effect
| Raw material is formed | 0.7A/0.3B | 0.8A/0.2B |
| Temperature of reaction, ℃ | 400 | 450 |
| Weight space velocity, h -1 | 3.0 | 0.5 |
| System pressure, MPa | 2.5 | 1.5 |
| Liquid yield, wt% | 93.9 | 98.2 |
| Methylbenzene selective, mol% | 80.1 | 81.2 |
Annotate: A represents benzene, and B is for methyl alcohol.
[embodiment 10]
Consist of 0.1%Rh-1.0%Sn-1.0%B/60%ZSM-5/5%TiO in weight
2/ 35%Al
2O
3Catalyzer J effect down, be that 5.45 coking benzene and moisture 2% Sweet natural gas system methyl alcohol are raw material with freezing point, react, reaction conditions and result see table 10:
Table 10 benzene and methyl alcohol is reaction result under catalyzer J effect
| Raw material is formed | 0.7A/0.3B | 0.5A/0.5B |
| Temperature of reaction, ℃ | 500 | 550 |
| Weight space velocity, h -1 | 2.5 | 1.0 |
| System pressure, MPa | 2.0 | 3.5 |
| Liquid yield, wt% | 98.9 | 91.3 |
| Methylbenzene selective, mol% | 78.8 | 77.1 |
Annotate: A represents benzene, and B is for methyl alcohol.
[embodiment 11]
Consist of 5.0%H in weight
3PO
4/ 60%ZSM-5/40%Al
2O
3Catalyzer K effect down, be that 5.40 benzene and moisture 2% system methyl alcohol are that raw material reacts with freezing point, reaction conditions and result see table 11:
Table 11 benzene and methyl alcohol is reaction result under the sieve catalyst effect
| Raw material is formed | 0.6A/0.4B | 0.8A/0.2B |
| Temperature of reaction, ℃ | 400 | 450 |
| Weight space velocity, h -1 | 5.0 | 2.0 |
| System pressure, MPa | 2.0 | 3.0 |
| Liquid yield, wt% | 97.4 | 97.2 |
| Methylbenzene selective, mol% | 79.6 | 81.5 |
Annotate: A represents benzene, and B is for methyl alcohol.
[embodiment 12]
Consist of 50%ZSM-5/50%SiO in weight
2Catalyzer L effect down, be that 5.40 benzene is that raw material reacts with containing anhydrous methanol with freezing point, reaction conditions and result see table 10:
Table 12 benzene and methyl alcohol is reaction result under the sieve catalyst effect
| Raw material is formed | 0.5A/0.5B | 0.7A/0.3B |
| Temperature of reaction, ℃ | 500 | 600 |
| Weight space velocity, h -1 | 0.5 | 2.5 |
| System pressure, MPa | 2.5 | 1.5 |
| Liquid yield, wt% | 93.3 | 96.4 |
| Methylbenzene selective, mol% | 77.1 | 81.3 |
Annotate: A represents benzene, and B is for methyl alcohol.
Claims (9)
1. the method for a benzene and methyl alcohol or dme system grade oil toluene is a raw material with benzene and methyl alcohol or dme, 250～600 ℃ of temperature of reaction, and reaction pressure 0.05～5.0MPa, raw material weight air speed 0.3～15h
-1Under the condition, alkylated reaction takes place in raw material on solid acid catalyst, generates grade oil toluene.
2. according to the method for the said benzene of claim 1 and methyl alcohol or dme system grade oil toluene, it is characterized in that said benzene freezing point is greater than 5.35.
3. according to the method for the said benzene of claim 1 and methyl alcohol or dme system grade oil toluene, it is characterized in that allowing to contain in said methyl alcohol or the dme by weight water less than 80%.
4. according to the method for the said benzene of claim 1 and methyl alcohol or dme system grade oil toluene, methyl alcohol or dme content are 5～65% in the raw material beyond it is characterized in that dewatering by weight percentage.
5. according to the method for the said benzene of claim 1 and methyl alcohol or dme system grade oil toluene, methyl alcohol or dme content are 10～45% in the raw material beyond it is characterized in that dewatering by weight percentage.
6. according to the method for the said benzene of claim 1 and methyl alcohol or dme system grade oil toluene, it is characterized in that used solid acid catalyst is selected from least a in the molecular sieve of ZSM-5, ZSM-12, mordenite, USY, beta-molecular sieve, UZM molecular sieve, EU-1 molecular sieve or MCM-41; Solid acid catalyst contains at least a in the metallic element that is selected from Mg, Ca, Ba, Zn, Ga, Mo, Ni, Co, W, Cu, Fe, Zr, Ti, Pt, Pd, Sn, Pb, La or Ce; Solid acid catalyst contains at least a in the non-metallic element that is selected from P, S, Cl, B.
7. according to the method for the said benzene of claim 1 and methyl alcohol or dme system grade oil toluene, it is characterized in that temperature of reaction is 300-500 ℃, reaction pressure is 0.1～4.0MPa, raw material weight air speed 0.5～5.0h
-1
8. according to the method for the said benzene of claim 1 and methyl alcohol or dme system grade oil toluene, it is characterized in that temperature of reaction is 350～450 ℃, reaction pressure is 0.5～3.0MPa, raw material weight air speed 0.8～3.0h
-1
9. according to the method for the said benzene of claim 1 and methyl alcohol or dme system grade oil toluene; It is characterized in that can feeding in the reaction system one or more and be selected from gases such as hydrogen, nitrogen, methane, carbon monoxide, carbonic acid gas as carrier gas, the mol ratio of benzene is less than 10.0 in carrier gas and the raw material.
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| CN103785461A (en) * | 2012-11-01 | 2014-05-14 | 中国石油化工股份有限公司 | Catalyst for alkylation of toluene and methanol, and preparation method and application thereof |
| CN107206365A (en) * | 2015-01-22 | 2017-09-26 | 托普索公司 | For converting methanol into the method for being suitable as gasoline or mixed material |
| CN108435246A (en) * | 2018-02-01 | 2018-08-24 | 浙江工业大学 | A kind of preparation method of multi-stage porous same order elements Ga-ZSM-5 molecular sieve catalysts |
| CN110026234A (en) * | 2019-04-29 | 2019-07-19 | 惠生工程（中国）有限公司 | A kind of alkylation catalyst and its preparation method and application |
| CN112888658A (en) * | 2018-08-24 | 2021-06-01 | 罗地亚经营管理公司 | Microporous crystalline aluminotitanosilicate zeolite, process for producing the same, and use thereof |
| CN114805144A (en) * | 2022-05-20 | 2022-07-29 | 广州市浪奇实业股份有限公司 | Hard water resistant alkylbenzene sulfonate and its preparation method and use |
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