CN102746099A - Method and device for preparing dimethylbenzene by alkylating benzene, methylbenzene and methanol - Google Patents
Method and device for preparing dimethylbenzene by alkylating benzene, methylbenzene and methanol Download PDFInfo
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- CN102746099A CN102746099A CN2012102331692A CN201210233169A CN102746099A CN 102746099 A CN102746099 A CN 102746099A CN 2012102331692 A CN2012102331692 A CN 2012102331692A CN 201210233169 A CN201210233169 A CN 201210233169A CN 102746099 A CN102746099 A CN 102746099A
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- toluene
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Abstract
The invention relates to a method for preparing dimethylbenzene by alkylating benzene, methylbenzene and methanol. The method comprises the following process steps of: (1) mixing raw materials of benzene, methylbenzene, circulating benzene and methylbenzene with the methanol, wherein the circulating benzene and methylbenzene are recovered by rectification, carrying out heat exchange on mixed materials and materials at an alkylated reactor outlet, heating the materials subjected to heat exchange to reach the alkylated reaction temperature and then allowing the material to enter the alkylated reactor and carrying out an alkylation reaction to obtain a product in the presence of a catalyst; and (2) enabling the product to enter a methylbenzene-removing tower for rectifying and separating; cooling a mixture of the benzene, the methylbenzene and water at the top of the tower and then carrying out oil-water separation, enabling oil phase to return to the alkylated reactor for circulating reaction; treating water phase and then recycling; and enabling oil at the bottom of the tower to enter a dimethylbenzene rectifying tower for rectifying and separating to obtain mixed dimethylbenzene and heavy aromatic as products.
Description
Technical field
The present invention relates to the production technology of petrochemicals, concrete strategic point is said and is related to a kind of method and apparatus by benzene, toluene and methanol alkylation system YLENE.
Background technology
YLENE is important aromatic hydrocarbons.Wherein p-Xylol mainly is used for producing terephthalic acid, and then produces the polyester raw material ethylene glycol terephthalate.M-xylene is used for producing m-phthalic acid, and o-Xylol is produced phthalic anhydride, and then produces various plastic plasticizers.
At present the topmost production approach of aromatic hydrocarbons is a naphtha reforming, obtains aromatic hydrocarbons mixture, and through processes such as absorption, freezing, rectifying, by-product passes through process combination such as isomerizing, disproportionation again.Said product that acquisition conforms to quality requirements.That is to say the extension processing of whole dependence oil.Because oil is Nonrenewable resources, the STRATEGIES OF SUSTAINABLE DEVELOPMENT economic viewpoint has proposed how to maximally utilise renewable resources or obtain desired product from new raw material route to us.
With methyl alcohol is alkylating raw material, and on phenyl ring, connecting methyl, to obtain heavier aromatic hydrocarbons be exactly a good way.Benzene and toluene also can obtain from the deep processing of coal not only from oil.On the other hand, because the methanol industry starting is early, raw material sources are wide, technology maturation, and the domestic production ability is superfluous.As adopt should technology production than heavy aromatics, both can replenish the deficiency of naphtha reforming product, on cost, have competitive power, also realized of the transfer of Coal Chemical Industry product to petrochemicals.
Both at home and abroad very early in the technological development of carrying out aspect aromatic hydrocarbons-methanol alkylation, the having of comparative maturity:
Mobil company report adopts P/HZSM-5 to make catalyzer, hydro condition; 600 ℃ of temperature of reaction, pressure 0.28MPa, WHSV4h-1; The molecular ratio of toluene and methanol/water/hydrogen is 2/1/6/6, methanol conversion 97.8%, toluene conversion 28.4%; PX selectivity 96.8%, the following lighter hydrocarbons of by-product C5 are less than 1%.
Indian Oil Corporation (IPCC) cooperates with GCT, has developed GT-TO-IAIKSM toluene methylation technology, has allegedly built up the PX device of 200Kt/a (200,000 tons/year).This technology adopts high silica zeolite catalyst, and temperature of reaction 400-450 ℃, pressure 0.1-0.5MPa, the mass ratio of toluene and methanol are 1.35/1, and the PX selectivity is more than 85%, single-pass operation cycle 6-12 month.
Domestic Dalian Chemistry and Physics Institute is a raw material with methyl alcohol and toluene; Adopt fluidized-bed reactor, producing PX output ethene, propylene simultaneously, catalyzer is a zeolite molecular sieve; Toluene conversion 20%; Methanol conversion 98-100%, p-Xylol in xylene isomer selectivity greater than 99%, the second propylene in lower carbon number hydrocarbons selectivity greater than 90%.At present in the lab scale stage.
Though aspect aromatic hydrocarbons-methanol alkylation, obtain certain progress at present both at home and abroad, be toluene and methanol alkylation system YLENE mostly, benzene, toluene parallel feeding or the independent charging of benzene and methanol alkylation system YLENE technology there be limited evidence currently of have relevant report.
Chinese patent " method of the synthetic YLENE of a kind of benzene and methanol alkylation " (CN102101818); Disclosing a kind of is raw material with benzene and methyl alcohol; In fixed-bed reactor, under the effect of the HMCM-56 of modification sieve catalyst, the method for the synthetic YLENE of benzene and methanol alkylation.
This method has only solved the problem of single raw material alkylation to prepare toluene.
Summary of the invention
The objective of the invention is to overcome the prior art defective a kind of method and apparatus by benzene, toluene and methanol alkylation system YLENE is provided.
The present invention realizes according to following proposal:
A kind of method by benzene, toluene and methanol alkylation system YLENE comprises following process step:
(1) recycle benzene that reclaims of benzene feedstock and toluene, rectifying and toluene together with methanol mixed; Mixed material warp and the heat exchange of alkylation reactor outlet material;, heating gets into alkylation reactor after reaching the alkylated reaction temperature again; Under the catalyzer existence condition, carry out alkylated reaction, obtain resultant;
(2) resultant gets into and to take off toluene tower and carry out rectifying separation, and the mixture of overhead benzene, toluene and water carries out oily water separation after cooling, and oil phase returns the alkylation reactor circulating reaction, and water is reuse after treatment; Oil entering xylene distillation tower carries out rectifying separation at the bottom of the tower, obtains xylol and heavy aromatics as product;
To take off the isolated recycle benzene of toluene tower, toluene and after fresh feed benzene, toluene mixed, again with methanol mixed, the mol ratio between recycle feed and the fresh feed was 1-10: 1;
Benzene and toluene can be arbitrary proportion in the fresh feed, comprise the independent charging of benzene or toluene;
In the described material that carries out alkylated reaction, the mol ratio between benzene and the methyl alcohol is 1-20: 1, and the mol ratio between toluene and the methyl alcohol is 1-10: 1;
The pressure of described alkylated reaction is 0.01-1.0Mpa, and temperature is 300-500 ℃, and the total air speed of raw material weight is 0.1-5h-1;
Said catalyzer is the modified ZSM-5 type zeolite [molecular sieve.
A kind of device by benzene, toluene and methanol alkylation system YLENE; Mainly by process furnace (3), alkylation reactor (5), take off toluene tower (6), xylene distillation tower (9) combines through pipeline and utility appliance according to technology; Wherein be filled with fixed bed catalyst in the alkylation reactor; The outlet that it is characterized in that process furnace (3) inserts alkylation reactor (5) top through pipeline; Alkylation reactor (5) outlet at bottom pipeline inserts through heat exchanger (2) and reboiler (8) and takes off toluene tower (6) middle part, takes off toluene tower (6) bottom and inserts xylene distillation tower (9) middle part by pipeline.
Method of the present invention compare with existing method have benzene, toluene conversion is high, benzene, toluene ratio can be regulated arbitrarily in the raw material, the advantage that the YLENE yield is high.Device of the present invention has facility compact, and flow process is smooth and easy, the characteristics that are easy to control.
Description of drawings
Fig. 1 is a basic flowsheet of coal preparation of the present invention, and among the figure, the meaning of each label is following:
1 vaporizer
2 interchanger
3 process furnace
4 vaporizers
5 alkylation reactors
6 take off toluene tower
7 return tanks
8 reboilers
9 xylene distillation towers
10 refluxing xylene jars
11 fresh feeds
12 methyl alcohol
13 fuel gas
14 sewage
15 thermal oils
16 sewage
17 xylol
18 heavy aromaticss
Embodiment
As shown in Figure 1, concrete process step of the present invention is following:
1, fresh feed benzene, toluene and recycle benzene, toluene mixing from taking off toluene tower; Behind gasifier (1), interchanger (2), get into charging process furnace (3) again and be heated to temperature of reaction, the methyl alcohol that then comes out with gasifier (4) is together sent into alkylation reactor (5) and is reacted.Reaction product gets into piptonychia benzene tower (6) after interchanger (2), piptonychia benzene tower bottom reboiler (8) heat exchange.
2, after alkylation reaction product got into and takes off toluene tower (6), the cat head vapour phase got into and takes off toluene tower return tank (7) through the complete condenser condensation.In return tank (7); The uncooled lighting end gas gas that acts as a fuel gets into fuel gas system, liquid abundant static layering in return tank, and water enters sewage work; The oil phase partial reflux, part is returned the alkylation feed system as recycle benzene, methylbenzene raw material.Xylene distillation tower (9) is sent in the heavy constituent of piptonychia benzene tower bottom.
3, take off toluene tower (6) tower at the bottom of heavy constituent after heat exchange, get into xylene distillation tower (9).Xylene distillation top of tower vapour phase gets into benzenol hydrorefining return tank (10) through the complete condenser condensation, partial reflux, and part is removed the xylol storage tank as the finished product; Tower bottom obtains C9 and above heavy aromatics, is sent to the heavy aromatics storage tank.
Embodiment 1
Adopting benzene separately is raw material, with methanol alkylation reaction system YLENE.Fresh feed and recycle feed mol ratio are 1: 3-6; Total benzene, methylbenzene raw material and methyl alcohol mol ratio are 4-8: 1; The pressure of reaction is 0.5-0.6Mpa; Temperature is 400-450 ℃, and the total air speed of raw material weight is 0.5-1h-1, produce meet " oil xylol national standard " (GB/T3470-2010) in the YLENE of 3 ℃ of xylol product standards.
Embodiment 2
Adopt benzene and toluene parallel feeding, with methanol alkylation reaction system YLENE.The mol ratio of toluene and benzene is 1: 1 in the fresh feed; Fresh feed and recycle feed mol ratio are 1: 2-4; Total raw material and methyl alcohol mol ratio are 3-5: 1, and the pressure of reaction is 0.5-0.6Mpa, temperature is 400-450 ℃; The total air speed of raw material weight is 1-2h-1, produce meet " oil xylol national standard " (GB/T3470-2010) in the YLENE of 3 ℃ of xylol product standards.
Embodiment 3
Adopt benzene and toluene parallel feeding, with methanol alkylation reaction system YLENE.The mol ratio of toluene and benzene is 2: 1 in the fresh feed; Fresh feed and recycle feed mol ratio are 1: 1-2; Total raw material and methyl alcohol mol ratio are 2-4: 1, and the pressure of reaction is 0.5-0.6Mpa, temperature is 400-450 ℃; The total air speed of raw material weight is 2-3h-1, produce meet " oil xylol national standard " (GB/T3470-2010) in the YLENE of 3 ℃ of xylol product standards.
Claims (7)
1. method by benzene, toluene and methanol alkylation system YLENE comprises following process step:
(1) recycle benzene that reclaims of benzene feedstock and toluene, rectifying and toluene together with methanol mixed; Mixed material warp and the heat exchange of alkylation reactor outlet material;, heating gets into alkylation reactor after reaching the alkylated reaction temperature again; Under the catalyzer existence condition, carry out alkylated reaction, obtain resultant;
(2) resultant gets into and to take off toluene tower and carry out rectifying separation, and the mixture of overhead benzene, toluene and water carries out oily water separation after cooling, and oil phase returns the alkylation reactor circulating reaction, and water is reuse after treatment; Oil entering xylene distillation tower carries out rectifying separation at the bottom of the tower, obtains xylol and heavy aromatics as product.
2. the method for claim 1 is characterized in that taking off the isolated recycle benzene of toluene tower, toluene and after fresh feed benzene, toluene mixed, again with methanol mixed, the mol ratio between recycle feed and the fresh feed was 1-10: 1.
3. the method for claim 1 is characterized in that benzene and toluene can be arbitrary proportion in the fresh feed, comprises the independent charging of benzene or toluene.
4. according to claim 1 or claim 2 method is characterized in that the mol ratio between benzene and the methyl alcohol is 1-20 in the described material that carries out alkylated reaction: 1, and the mol ratio between toluene and the methyl alcohol is 1-10: 1.
5. according to claim 1 or claim 2 method, the pressure that it is characterized in that described alkylated reaction is 0.01-1.0Mpa, and temperature is 300-500 ℃, and the total air speed of raw material weight is 0.1-5h-1.
6. according to claim 1 or claim 2 method is characterized in that said catalyzer is the modified ZSM-5 type zeolite [molecular sieve.
7. device by benzene, toluene and methanol alkylation system YLENE; Mainly by process furnace (3), alkylation reactor (5), take off toluene tower (6), xylene distillation tower (9) combines through pipeline and utility appliance according to technology; Wherein be filled with fixed bed catalyst in the alkylation reactor; The outlet that it is characterized in that process furnace (3) inserts alkylation reactor (5) top through pipeline; Alkylation reactor (5) outlet at bottom pipeline inserts through heat exchanger (2) and reboiler (8) and takes off toluene tower (6) middle part, takes off toluene tower (6) bottom and inserts xylene distillation tower (9) middle part by pipeline.
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Cited By (4)
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CN103467238A (en) * | 2013-08-23 | 2013-12-25 | 宁夏宝塔石化科技实业发展有限公司 | Production method for p-xylene |
CN104109065A (en) * | 2014-06-07 | 2014-10-22 | 宁夏宝塔石化科技实业发展有限公司 | Method of preparing xylene by alkylation of benzene and methanol |
CN105732293A (en) * | 2014-12-11 | 2016-07-06 | 中国石油天然气股份有限公司 | Separation device and separation method for alkylation reaction product of benzene and methanol |
CN107602321A (en) * | 2017-07-24 | 2018-01-19 | 陕西煤化工技术工程中心有限公司 | A kind of fluidized-bed process method of benzene and methanol alkylation production paraxylene |
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CN101624327A (en) * | 2009-08-14 | 2010-01-13 | 山西恒扬科技有限公司 | Method for preparing methylbenzene or dimethylbenzene by alkylating benzene with methanol |
CN102101818A (en) * | 2009-12-16 | 2011-06-22 | 中国石油天然气股份有限公司 | Method for synthesizing dimethylbenzene by alkylation of benzene and methanol |
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CN101624327A (en) * | 2009-08-14 | 2010-01-13 | 山西恒扬科技有限公司 | Method for preparing methylbenzene or dimethylbenzene by alkylating benzene with methanol |
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103467238A (en) * | 2013-08-23 | 2013-12-25 | 宁夏宝塔石化科技实业发展有限公司 | Production method for p-xylene |
CN103467238B (en) * | 2013-08-23 | 2016-08-10 | 宁夏宝塔石化科技实业发展有限公司 | A kind of production method of xylol |
CN104109065A (en) * | 2014-06-07 | 2014-10-22 | 宁夏宝塔石化科技实业发展有限公司 | Method of preparing xylene by alkylation of benzene and methanol |
CN104109065B (en) * | 2014-06-07 | 2016-01-06 | 宁夏宝塔石化科技实业发展有限公司 | A kind of method by benzene and methanol alkylation dimethylbenzene |
CN105732293A (en) * | 2014-12-11 | 2016-07-06 | 中国石油天然气股份有限公司 | Separation device and separation method for alkylation reaction product of benzene and methanol |
CN107602321A (en) * | 2017-07-24 | 2018-01-19 | 陕西煤化工技术工程中心有限公司 | A kind of fluidized-bed process method of benzene and methanol alkylation production paraxylene |
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