CN203513528U - Device for preparing toluene and m-cymene through 3-carene - Google Patents

Abstract

The utility model discloses a device for preparing toluene and m-cymene through 3-carene. The device comprises a fixed bed reactor, wherein the device is composed of a preheater, the fixed bed reactor, a condenser, a collector and a vacuum distillation tower, which are serially connected in sequence, and an A type catalyst and a B type catalyst are sequentially loaded in the fixed bed reactor along the material flow direction. The device is simple in process, efficiency and environmental-friendly, and the raw material is natural and renewable. Natural toluene and m-cymene with high purity can be prepared from a natural and environmental-friendly material.

Description

The device of being prepared toluene and an isopropyltoluene by 3-carene

Technical field

The utility model relates to turps deep processing and utilization field, relate in particular to by turps moiety 3-carene interlock system for toluene and isopropyltoluene process unit used, and product has natural equivalent attribute.

Background technology

The chemical name of 3-carene is 3,7,7-trimethylammonium dicyclo [4.1.0] heptan-3-alkene, and molecular formula is C ₁₀h ₁₆, relative molecular mass 136.24.3-carene is monoterpene component important in natural essential oil; there is special pine fragrance; can directly make spices uses; 3-carene has good chemical reactivity simultaneously; reactions such as oxidation, reduction, addition, isomery, formylation, hydroboration be can there is, by it, for the prepared a series of compounds of raw material, spices, agricultural chemicals, medicine and other fields are widely used in.

Turps is the topmost source of 3-carene, with the difference of the factors such as pine tree seeds, the age of tree and the place of production, there is larger difference in its content in turps, content in Qi India longleaf pine turps can be up to 50%, content in Scots pine turps also has 45% more than (chemistry of forest product and industry, 2011,31 (3): 122～126).Although China is gum turpentine big producing country, but in the turps that China produced in the past, 3-carene content is extremely low or do not contain 3-carene, so China never has 3-carene resource on a large scale, but in Yunnan Province, found that in recent years larger area is rich in the pinus khasys of 3-carene, (Nanjing Forestry University's journals: natural science edition such as Geng Shuxiang of forest-science academy, Yunnan, 2005, 29 (5): 85～87) by finding being collected in the composition research of the Lianghe of Yunnan Dehong and the pinus khasys rosin of two places, Luxi, wherein containing 3-carene, be respectively 8.52% and 20.11%, and the mean value of content in corresponding turps is respectively 19.47% and 34.88%.Li Si extensively waits (Sino-South African Forestry University of Science and Technology's journal, 2009,29 (4): 49～53), also by finding being collected in the research of more than 40 pinus khasys rosin sample of different areas, Yunnan, in high yield fat clone pinus khasys, 3-carene content can reach 38.02%.Along with increasing this type pine tree enters the plantations of resin tapping phase and more large-area similar seeds, the resource of 3-carene will be more and more abundanter, and appearing at of these resources also promoted the research that utilizes for 3-carene when having made up China 3-carene resource shortage.

Owing to limit by resource, in China for the research of 3-carene also in the starting stage, and external colleague has done in this regard a large amount of work and has obtained abundant achievement.From existing bibliographical information, the achievement in research of relevant 3-carene more concentrates on response characteristic and the product application aspect of its oxidation, addition, these two kinds of reactions all betide on the six-ring or two key of 3-carene, and resultant is all the compound that remains with triatomic ring structure.And relatively less for the research of its another important functional group triatomic ring, this is mainly because the intramolecular triatomic ring of 3-carene has the characteristic similar with aromatic ring, structure is comparatively stable, generally be difficult for reacting, some existing achievement in research proof isomerization reactions tend to cause the fracture of triatomic ring in 3-carene molecule, along with fracture position and subsequent reactions mode difference, resultant also can be ensued variation, in most cases generates and in product, all contains Paracymene and an isopropyltoluene.US3407242(US, 3407242, the technique of 1968-10-22) inventing is that 3-carene is at H ₂with under the acting in conjunction of the hydrogenation catalyst such as Pd/C, Raney Ni, first partly change 4-carene into, then continue to be heated to 180 ℃ of left and right, the mixture of the 4-carene isomeric transition of generation Wei limonene, Paracymene and an isopropyltoluene etc.(Topics in Catalysis, 2004,27 (1-4): 143-155) mention with Pt-Al in article such as Swift ₂o ₃, Pt-C or Cr ₂o ₃-Al ₂o ₃for catalyzer can tautomerize to 3-carene the mixture of Paracymene and an isopropyltoluene.Krishnasany etc. (Can.J.Chem, 1977,55:3046～3049) are respectively with Cr ₂o ₃and Cr ₂o ₃-Al ₂o ₃for catalyzer, investigate the isomery of 3-carene at 450 ℃ and 400 ℃ and generated product situation, found that the dehydrogenation of 3-carene is converted into Paracymene and an isopropyltoluene under this technique, the total yield of two kinds of compounds is 70%.(the Studies in Surface Science and Catalysis such as Buhl, 1999,121:191-196) take respectively the Si that is carried on the Pd through Ce modification on zeolite molecular sieve and crosses through the abundant immersion treatment of Pd is converted into 3-carene to take Paracymene as main mix products as catalyzer, wherein the selectivity of Paracymene in product can reach 60%, and Main By product is terpinolene etc.Above-mentioned research shows, under existing processing condition, 3-carene can tautomerize to an isopropyltoluene, but be all in most cases to obtain a kind of isopropyltoluene and other mixture that becomes to be grouped into, and these compositions are because character is similar each other, are difficult to carry out separation, particularly as the Paracymene of its isomers, substantially cannot be separated by ordinary method, therefore, be difficult to obtain highly purified single compound.

Toluene is one of the most basic industrial chemicals, a large amount of as solvent and stop bracket gasoline additive, also be the important source material of synthetic other organic compound, by its prepared Chemicals, be widely used in the industries such as dyestuff, medicine, agricultural chemicals, spices, synthetic materials simultaneously.The at present production of toluene mainly relies on petroleum industry, and day by day exhausted along with petroleum resources found substitute and seemed particularly important.

Between isopropyltoluene, chemical name is 1-methyl-3-isopropyl benzene, is a kind of important Chemicals, can directly make solvent and use, and also can be used for metal processed and puts photo etching, synthetic resins, terephthalic acid, cresylol, acetone etc. on the skin.At present, between isopropyltoluene mainly by toluene and propylene, by alkylated reaction, prepared, it is raw material that American UOP-Hercules technology be take toluene and propylene, adopt solid phosphoric acid catalyst, first synthesize the isopropyltoluene mixture (right:: neighbour is 33: 23: 44) that is rich in ortho position, through aluminium trichloride complex catalyst isomerization, obtaining take meta-isomer is again main mix products (right:: adjacent to being 33: 64: 3), this techniqueflow is long, material consumption energy consumption is large, and the seriously polluted (petrochemical technology of burn into, 1998,5 (2): 125～127).(the petroleum journal (refining of petroleum) such as Li Shuwen, 1995,11 (2): 24～31), on this basis by improving catalyzer, propose a kind of new preparation technology, the ZSM-5 of modification of take is less than 1.0 as catalyzer one-step synthesis ortho position content, between pair than the mixing isopropyltoluene that is greater than 2.0.Guo Rusheng etc. (gas chemical industry, 1995,20 (3): 39～43) by the TPA catalyzer that adopts large pore zeolite to prepare through modulation for toluene-propylene alkylation reaction, the mixture of three kinds of isopropyltoluenes of one-step synthesis, wherein adjacent:: to being 4: 63: 33.Can find out that above method generates the mixture that product is all three kinds of isomer, and their isomerss are each other difficult to, by general method separation, expect that highly purified one matter is very difficult.

Summary of the invention

The purpose of this utility model is to provide a kind of device of being prepared toluene and an isopropyltoluene by 3-carene.Use this device can succinctly obtain efficiently highly purified toluene and an isopropyltoluene, products obtained therefrom has natural equivalent attribute.

The technical solution of the utility model is: a kind of device of being prepared toluene and an isopropyltoluene by 3-carene, comprise fixed-bed reactor, by preheater, fixed-bed reactor, condenser, collector and vacuum rectifying tower, be composed in series successively, in described fixed-bed reactor, along flow direction of material, load successively A type catalyzer and Type B catalyzer.

Described A type catalyzer and the volume ratio of Type B catalyzer are 1: 2～2: 1.

Described preheater comprises gasification installation, and feeding unit, diffuser, temperature measuring equipment, air-out apparatus are set respectively on gasification installation.

Described gasification installation is provided with heating jacket outward.

Described fixed-bed reactor are provided with heating jacket outward.

Reaction principle of the present utility model and reaction scheme are expressed as follows with chemical equation:

Operational path that the utility model provides comprises following key step:

1. catalyst powder is broken to the particle of 20～30 order sizes, by usage ratio, evenly fills in reactor and (by flow direction of material, from import to outlet, be followed successively by A type catalyzer and Type B catalyzer);

2. reactor is imported and exported respectively and disposed carrier gas system and be connected with preheater and the condenser of feed system, control carrier gas and arrive target flow, reactor is heated to predetermined temperature of reaction;

3. preheater is heated to 150 ℃～200 ℃, and make 3-carene by feed system slowly at the uniform velocity enter into preheater, after gasification, under carrier gas is led, enter reactor;

4. complete reacted material and flow out from reactor, by condenser, liquefy, collection distillates liquid and is mix products;

5. gained mix products is done to rectification process, obtain single toluene and an isopropyltoluene product.

Beneficial effect

1. the utility model has been developed brand-new, an efficient 3-carene and has been utilized approach;

2. the utility model provides a kind of new natural reproducible raw material of preparing natural equivalent toluene and an isopropyltoluene;

3. the utility model provides a kind of easy to operate, pollution-free, and material loss is little, product purity is high, preparation technology's system of renewable, the eco-friendly toluene of resource and an isopropyltoluene and corresponding preparation facilities.

Accompanying drawing explanation

Fig. 1 is reactive system and the setting drawing of being prepared toluene and an isopropyltoluene by 3-carene described in the utility model, mainly 4 unit such as preheater (consisting of 1～5 several parts), fixed-bed reactor (6), condenser (7) and collectors (8), consists of.In figure, (1) is gasification installation, and (2) are feeding unit, and (3) are diffuser, and (4) are temperature measuring equipment, and (5) are air-out apparatus, and (6) are fixed-bed reactor, and (7) are condenser, and (8) are collector.Gasification installation and fixed-bed reactor are all equipped with respectively corresponding heating system, A type and the loading sequence of Type B catalyzer in reactor for being followed successively by A section and B section from import to outlet by flow direction of material, at the front end of fixed-bed reactor, fill A type catalyzer, in the rear end of fixed-bed reactor, fill Type B catalyzer.

Embodiment

Embodiment

A kind of device of being prepared toluene and an isopropyltoluene by 3-carene, comprise fixed-bed reactor, by preheater, fixed-bed reactor, condenser, collector and vacuum rectifying tower, be composed in series successively, in described fixed-bed reactor, along flow direction of material, load successively A type catalyzer and Type B catalyzer.Described A type catalyzer and the volume ratio of Type B catalyzer are 1: 2～2: 1.Described preheater comprises gasification installation, and feeding unit, diffuser, temperature measuring equipment, air-out apparatus are set respectively on gasification installation.Described gasification installation is provided with heating jacket outward.Described fixed-bed reactor are provided with heating jacket outward.

By A type catalyst Pt-Al ₂o ₃(carrying platinum amount is carrier A l ₂o ₃1% of quality, lower same) and Type B catalyst Z SM-5 type molecular sieve (SiO ₂/ Al ₂o ₃=50) be all crushed to the particle of 20～30 order sizes, load respectively 6.3cm ³(8cm) and 12.5cm ³(16cm) in length is 30cm, the internal diameter crystal reaction tube that is 1cm as fixed-bed reactor; Import and export and to be connected with the reaction flask and the prolong that dispose ventpipe, constant pressure funnel and temperature controller respectively, and to regulate carrier gas flux be 15mL/min, reaction tubes is heated to 300 ℃; The 3-carene that is 92.6% by content, by slow the splashing in the reaction flask that is heated in advance 190 ℃ of left and right at the uniform velocity of constant pressure funnel, enters reaction tubes with carrier gas after the gasification of 3-carene, distillates after completing reaction, cooling by prolong, collects distillate; Make GC and analyze, in distillate, toluene, dimethylbenzene, ethyl methyl benzene and an isopropyltoluene content are respectively 27.8%, 2.3%, 2.6% and 52.5%.Distillate enters after vacuum rectifying tower, at rectification temperature, be that 60 ℃～70 ℃, the pressure of rectifying are collected while being 0.006MPa and obtained the toluene that purity is greater than 99.0%, rectification temperature be 80 ℃～90 ℃, the pressure of rectifying collect while being 0.001MPa obtain purity be greater than 95.0% between isopropyltoluene.

Claims (5)

1. a device of being prepared toluene and an isopropyltoluene by 3-carene, comprise fixed-bed reactor (6), it is characterized in that, by preheater, fixed-bed reactor (6), condenser (7), collector (8) and vacuum rectifying tower, be composed in series successively, in described fixed-bed reactor (6), along flow direction of material, load successively A type catalyzer and Type B catalyzer.

2. the device of being prepared toluene and an isopropyltoluene by 3-carene according to claim 1, is characterized in that, described A type catalyzer and the volume ratio of Type B catalyzer are 1: 2～2: 1.

3. the device of being prepared toluene and an isopropyltoluene by 3-carene according to claim 1, it is characterized in that, described preheater comprises gasification installation (1), and feeding unit (2), diffuser (3), temperature measuring equipment (4), air-out apparatus (5) are set respectively on gasification installation (1).

4. the device of being prepared toluene and an isopropyltoluene by 3-carene according to claim 3, is characterized in that, described gasification installation is provided with heating jacket outward.

5. the device of being prepared toluene and an isopropyltoluene by 3-carene according to claim 1, is characterized in that, described fixed-bed reactor are provided with heating jacket outward.

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