CN107382645B - Synthetic process method and device of isoprene - Google Patents
Synthetic process method and device of isoprene Download PDFInfo
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- CN107382645B CN107382645B CN201710533858.8A CN201710533858A CN107382645B CN 107382645 B CN107382645 B CN 107382645B CN 201710533858 A CN201710533858 A CN 201710533858A CN 107382645 B CN107382645 B CN 107382645B
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- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
- C07C1/207—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms from carbonyl compounds
- C07C1/2076—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms from carbonyl compounds by a transformation in which at least one -C(=O)- moiety is eliminated
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
- C07C45/38—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups being a primary hydroxyl group
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- C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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Abstract
The invention discloses a synthesis process method of isoprene, which comprises the steps of oxidizing methanol serving as a raw material to obtain a formaldehyde raw material gas, enabling the formaldehyde raw material gas to be in countercurrent contact with isooctanol in an absorption synthesis tower, performing two-stage absorption synthesis through a filler section and a tower plate section to obtain an alcohol-aldehyde condensate, extracting to obtain an organic phase, dehydrating to control the water content to be below 1% by mass, continuously feeding the organic phase into an analytical tower for decomposition, mixing the organic phase with preheated MTBE raw material gas to obtain MTBE/formaldehyde/isobutylene raw material mixed gas, and sequentially performing fluidized bed reaction, cooling absorption, compression condensation, isobutylene separation and the like to obtain an isoprene product. The invention also produces byproduct isobutene in the process and recycles the isobutene, compared with the traditional domestic C5 extraction method, the method has the advantages of difficult raw material source, wide MTBE raw material source, short flow, simple separation, low energy consumption, high product quality and the like, and is suitable for large-scale industrial production.
Description
Technical Field
The invention belongs to the technical field of energy and chemical engineering, and particularly relates to a synthetic preparation method of isoprene.
Background
Isoprene, also known as 2-methyl-1, 3-butadiene, is a colorless, volatile liquid at ambient temperature. Dissolved in benzene, and easily dissolved in ethanol, diethyl ether and acetone to generate binary and ternary azeotropic compositions; isoprene is almost insoluble in water and forms an explosive mixture with air, with an explosion limit of more than 1.6%. Isoprene contains conjugated double bonds, is active in chemical property, is easy to generate homopolymerization and copolymerization reaction, and can react with a plurality of substances to generate a new compound. As the highest quality product of isoprene products, polymer grade isoprene is mainly used for producing cis-and trans-polyisoprene rubber, SIS (styrene-isoprene-styrene block copolymer), and is also the second monomer of butyl rubber. In addition, isoprene is widely used in the fields of pesticides, medicines, perfumes, adhesives and the like.
At present, the domestic production of polymer grade isoprene is mainly prepared by C5 separation, and because of the production process, raw material supply and the like, the yield can not meet the requirements of the development of isoprene downstream products in China, and the development of isoprene and downstream products is limited.
The existing synthesis method for preparing isoprene mainly comprises (1) an extraction method, wherein when ethylene is produced, a byproduct C5 fraction accounts for about 3% of the ethylene yield, and the isoprene content in the C5 fraction is 15-20%; (2) propylene dimerization process; (3) an isoamylene dehydrogenation method; (4) isobutylene-formaldehyde process; (5) acetone-acetylene process. The five synthetic methods have narrow raw material sources, complex process and high cost, and are difficult to meet the market demand of isoprene. Therefore, a synthetic method for comprehensively preparing isoprene with wide raw material sources, low energy consumption, low cost and less three-waste emission is needed.
In the conventional isobutene-formaldehyde method, water molecules in formaldehyde are easy to react to obtain isobutanol by reaction of isobutene and water, so that the yield is reduced, and more importantly, the isobutanol can damage the catalyst of isoprene.
Disclosure of Invention
The invention aims to: aiming at the existing problems and defects, the invention aims to provide an isoprene synthesis process method which has the characteristics of wide raw material source, small three-waste generation amount, easiness in treatment, low energy consumption and the like.
The technical scheme is as follows: in order to solve the technical problems, the invention adopts the following technical scheme: a synthetic process method of isoprene mainly comprises the following steps:
(1) Oxidizing methanol serving as a raw material in an oxidizer to prepare a formaldehyde raw material gas;
(2) Feeding formaldehyde feed gas into the bottom of an absorption synthesis tower, feeding isooctanol feed solution into the top of the absorption synthesis tower, allowing the formaldehyde feed gas to pass through a tower plate section of the absorption synthesis tower to contact with isooctanol-containing mixed solution sprayed from top to bottom for absorption reaction, allowing the formaldehyde gas which is not subjected to the absorption reaction to continuously rise to contact with the isooctanol feed material for further absorption reaction in a filler section, allowing an organic phase containing an alcohol-aldehyde condensate subjected to the absorption reaction and a water phase containing the formaldehyde solution to be statically layered at the bottom of the absorption synthesis tower, and feeding the organic phase to a subsequent process;
(3) Removing water from the organic phase in a dehydration tower, and controlling the water content to be below 1% (mass ratio);
(4) The dehydrated organic phase is sent to the middle part of an analytic tower, MTBE raw material liquid is sent from the top part of the analytic tower, the organic phase is analyzed at the middle-lower section of the analytic tower at 160-200 ℃ to obtain formaldehyde gas and isooctanol liquid, the isooctanol liquid flows downwards along a tower plate in the analytic tower and is recycled, and the formaldehyde gas rises along the tower plate of the analytic tower and is mixed with MTBE at the top of the tower to contact, exchange heat and gasify to obtain mixed gas of formaldehyde and MTBE;
(5) Preheating mixed gas of formaldehyde and MTBE, feeding the preheated mixed gas into a fluidized bed reactor, and continuously carrying out ether-aldehyde polymerization reaction under the action of a solid acid catalyst, wherein the reaction temperature is 300 +/-20 ℃;
(6) Cooling the reaction product by a cooling tower to obtain a gas-phase product containing isoprene and isobutene, and a liquid-phase product very easily containing methanol, formaldehyde and water, and returning the liquid-phase product to the step (1) for recycling; and separating the gas-phase product to obtain an isoprene product.
The technical scheme is improved, the gas-phase product obtained in the step (6) is firstly compressed and condensed into liquid, then isoprene and isobutene are obtained through rectification and separation, and the isobutene is recycled and sent to the desorption tower in the step (4) together with METBE.
In the improvement of the technical scheme, the solid catalyst takes SiO2, B2O3, AL2 (SO 4) 3, siO2-AL2O3 or B2O3-AL2O3 as a carrier and comprises one or a mixture of more of bismuth oxide, zirconium oxide, cerium oxide, calcium oxide and tantalum oxide.
In the improvement of the technical scheme, the aluminum oxide is gamma-AL 2O3 which is roasted at the temperature of 800 +/-50 ℃ and contains hydroxyl on the surface.
The improvement of the technical proposal is that the specific surface area of the solid catalyst is 400 to 500 square meters per gram, the bulk specific gravity is 0.45 plus or minus 0.05 grams per milliliter, the acidity is +3.2 to 3.5Pka, and the granularity is 40 to 120 meshes.
In the improvement of the technical scheme, the solid catalyst is composed of SiO2-AL2O3 or B2O3-AL2O3 as a carrier and zirconium oxide and tantalum oxide.
The invention also provides a synthesis process device of isoprene as described in claim 1, which comprises a formaldehyde oxidizer, an absorption synthesis tower, a rectifying tower, a dehydrating tower, a desorption tower, a fluidized bed reactor, a cooling absorption tower, a compression condenser, an isobutylene separation tower and a methanol separation tower, wherein the formaldehyde oxidizer is provided with a methanol inlet and a formaldehyde mixer gas outlet, the formaldehyde mixed gas outlet of the formaldehyde oxidizer is connected with a pipeline at the bottom of the absorption synthesis tower, the top, the upper part and the bottom of the absorption synthesis tower are respectively provided with a tail gas outlet, an isooctanol raw material inlet and an organic phase extraction port, the tail gas outlet is connected with the rectifying tower, the organic phase extraction port at the bottom of the absorption synthesis tower is connected with an inlet pipeline at the middle part of the dehydrating tower, and the bottom of the dehydrating tower is provided with an alcohol-aldehyde condensation product outlet and is connected with an inlet pipeline at the upper part of the desorption tower; the upper part, the top and the bottom of the desorption tower are respectively provided with an MTBE inlet, a feed gas outlet and an isooctanol outlet, the isooctanol outlet is connected with an isooctanol feed inlet circulating pipeline of the absorption synthesis tower, the feed gas outlet is sequentially connected with a fluidized bed reactor, a cooling absorption tower, a compression condenser and an isobutene separation tower pipeline, and the isooctanol outlet is connected with an isooctanol feed inlet pipeline at the top of the absorption synthesis tower; and the methanol separator is connected with an outlet of the cooling absorption tower and is circularly connected with a methanol inlet pipeline of the oxidizer.
Preferably, the absorption synthesis tower comprises an upper packing absorption tower and a lower tower plate absorption section, and the top of the absorption synthesis tower is also provided with a sprayer.
Preferably, a preheater is further provided before the MTBE inlet of the desorption tower.
Has the advantages that: compared with the prior art, the prior domestic C5 extraction method has difficult raw material sources, and the MTBE provided by the invention has wide raw material sources, has the characteristics of short flow, simple separation, low energy consumption, high product quality and the like, and is suitable for large-scale industrial production.
Drawings
FIG. 1 is a schematic process flow diagram of the synthetic process method of isoprene in the invention.
The system comprises a formaldehyde oxidizer 1, an absorption synthesis tower 2, a rectifying tower 3, a dehydrating tower 4, a resolving tower 5, a fluidized bed reactor 6, a compression condenser 7 and a preheater 8.
Detailed Description
The present invention is further illustrated by the following figures and specific examples, which are to be understood as illustrative only and not as limiting the scope of the invention, which is to be given the full breadth of the appended claims and any and all equivalent modifications thereof which may occur to those skilled in the art upon reading the present specification.
The solid catalyst can be prepared by modifying or directly synthesizing after purchasing a commercially available catalyst, and the specific method comprises the following steps: firstly, sodium silicate solution is treated by cation exchange resin to remove sodium ions so as to prepare silica sol, and ethylene glycol or urea (organic amine) is added into the silica sol and uniformly stirred so as to obtain uniform silica sol. In addition, dissolving metal aluminum powder (the particle size is preferably 50 mu m) in dilute hydrochloric acid to obtain aluminum sol, simultaneously preparing citrate of tantalum and zirconium, adding the citrate and the aluminum sol into the silica sol to obtain a precursor of the Si-AL-Zr-Ta catalyst, drying and dehydrating for 2-5 h at 60-180 ℃, finally, feeding the precursor into a muffle furnace to roast for 6h at different temperatures between 600-1000 ℃ to obtain an off-white blocky substance, and crushing and screening to obtain SiO2-AL2O3-ZrO2-Ta2O5 catalyst samples with the particle size of 100 meshes and different sintering temperatures. Wherein the mass ratio of each metal element is preferably Si: AL: zr: ta =2, 6, and the crystalline form of alumina is γ -type.
| Sample numbering | Sintering temperature | S BET (m 2 /g) | Bulk to weight ratio (g/ml) | Acidity (Pka) |
| 1 | 600 | 478 | 0.44 | +3.4 |
| 2 | 800 | 462 | 0.45 | +3.2 |
| 3 | 1000 | 320 | 0.48 | +3.5 |
The BET specific surface area test of the catalyst product shows that S BET And =400 to 500 square meters per gram, the sintering agglomeration of the powder is accelerated as the sintering temperature rises to 1000 ℃, and the sintering temperature is preferably 600 to 800 ℃.
Filtering, mixing and preheating quaternary gas of methanol, air, tail gas and water vapor to 110 ℃, sending the quaternary gas into a formaldehyde oxidizer to oxidize at 600-660 ℃, and obtaining formaldehyde mixed gas of 5KPa and 150 ℃ from the bottom of the formaldehyde oxidizer. Mixing formaldehyde and feeding the mixture into the bottom of an absorption synthesis tower, feeding isooctanol raw material liquid into the top of the absorption synthesis tower, allowing the formaldehyde mixed gas to pass through a tower plate section of the absorption synthesis tower to contact with isooctanol-containing mixed liquid sprayed from top to bottom for absorption reaction, allowing formaldehyde gas which is not subjected to the absorption reaction to continuously rise to contact with the isooctanol raw material for further absorption reaction in a filler section, and allowing the absorption reaction to obtain an organic phase containing an alcohol-aldehyde condensate and a water phase of the formaldehyde solution to be statically layered at the bottom of the absorption synthesis tower. The upper organic phase is pumped and sent into a dehydration tower for rectification dehydration, and the water content is controlled to be below 1% (the step is required, otherwise, the reverse reaction of isoprene is increased, so that the yield and the conversion rate of isoprene are reduced). Thermally decomposing the dehydrated organic phase in an analytical tower, heating and analyzing the organic phase after the organic phase enters the middle part of the analytical tower, simultaneously sending MTBE into the analytical tower, obtaining an analyzed isooctanol liquid phase from the bottom of the tower, and obtaining a formaldehyde/MTBE/isobutene gas raw material from the top of the tower. And the gaseous raw material of formaldehyde/MTBE/isobutene is sent into a reactor filled with the catalyst to react to obtain mixed gas of isoprene and isobutene, the mixed gas is cooled, compressed and condensed, and separated to obtain an isoprene product and isobutene serving as a reaction raw material, and the isobutene is circularly sent into an analytical tower to react with formaldehyde to continuously generate isoprene.
The reactor for isoprene in the invention preferably adopts a fluidized bed, and the synthesis reaction temperature of MTBE, isobutene and formaldehyde is 300-350 ℃. The reaction product withdrawn from the reactor mainly comprises isoprene, isobutylene, formaldehyde, methanol, MTBE and a small amount of water, and the condensed gas phase comprises isoprene and isobutylene in a gas phase and methanol, formaldehyde and water in a liquid phase. The liquid phase is dealcoholized by rectification, and dilute formaldehyde is obtained from the tower bottom as a byproduct; the gas phase mainly comprises isoprene and isobutene and is prepared by separation and refining.
Taking a polymer grade isoprene project with a yield of 5 ten thousand tons as an example, taking a No. 2 catalyst sample as an example, the conversion rate of MTBE can reach 84.3%, the yield of isoprene can reach 75.5%, and the yield of isobutene can reach 66.5%. The highest conversion is 77.5% higher compared with the traditional olefine aldehyde method. And the consumption per ton of isoprene product is: 1.7 tons of MTBE, 0.22 ton of formaldehyde, 1.0 ton of catalyst, 9.0 tons of 1.0MPaG steam, 440 cubic meters of circulating water, 89KWH of electric quantity, 1.3KG of fuel gas and 90N cubic meters of compressed nitrogen. And the traditional C5 fraction by the olefine aldehyde method needs 4.68 tons, 0.76 ton of formaldehyde, 11.5 tons of steam, 120KWH of electric quantity, 72KG of fuel, 520 cubes of cooling circulating water and 10 cubes of process water, and the cost of the required raw materials is obviously higher. The key point is that the MTBE raw material has wider sources and can meet the market demand of isoprene polymerization.
The technical indexes of the isoprene synthesis process relative to other process methods are as follows:
Claims (7)
1. a synthetic process method of isoprene mainly comprises the following steps:
(1) Oxidizing methanol serving as a raw material in an oxidizer to prepare a formaldehyde raw material gas;
(2) Feeding formaldehyde feed gas to the bottom of an absorption synthesis tower, feeding isooctanol feed liquid to the top of the absorption synthesis tower, allowing the formaldehyde feed gas to pass through a tower plate section of the absorption synthesis tower to contact with isooctanol-containing mixed liquid sprayed from top to bottom for absorption reaction, allowing the formaldehyde gas which is not subjected to the absorption reaction to continuously rise to contact with the isooctanol feed material in a filler section for further absorption reaction, allowing an organic phase containing an alcohol-aldehyde condensate subjected to the absorption reaction and a water phase containing the formaldehyde solution to be statically layered at the bottom of the absorption synthesis tower, and feeding the organic phase to a subsequent process;
(3) Removing water from the organic phase in a dehydration tower, and controlling the water content to be below 1%;
(4) The dehydrated organic phase is sent to the middle part of an analytical tower, MTBE raw material liquid is sent from the top of the analytical tower, the organic phase is analyzed at the middle-lower section of the analytical tower at 160-200 ℃ to obtain formaldehyde gas and isooctanol liquid, the isooctanol liquid flows down along the inner tower plate of the analytical tower and is recycled, and the formaldehyde gas rises along the tower plate of the analytical tower and is mixed, contacted, heat-exchanged and gasified with MTBE at the top of the tower to obtain mixed gas of formaldehyde and MTBE;
(5) Preheating mixed gas of formaldehyde and MTBE, feeding the preheated mixed gas into a fluidized bed reactor, and continuously carrying out ether-aldehyde polymerization reaction under the action of a solid catalyst, wherein the reaction temperature is 300 +/-20 ℃;
(6) Cooling the reaction product by a cooling tower to obtain a gas-phase product containing isoprene and isobutene and a liquid-phase product containing methanol, formaldehyde and water, and returning the liquid-phase product to the step (1) for recycling; and separating the gas-phase product to obtain an isoprene product.
2. The method of claim 1, wherein: and (4) compressing and condensing the gas-phase product obtained in the step (6) into a liquid state, rectifying and separating to obtain isoprene and isobutene, recycling the isobutene and sending the isobutene and METBE into the desorption tower in the step (4).
3. The method of claim 1, wherein: the solid catalyst takes SiO2, B2O3, AL2 (SO 4) 3, siO2-AL2O3 or B2O3-AL2O3 as a carrier and comprises one or a mixture of more of bismuth oxide, zirconium oxide, cerium oxide, calcium oxide and tantalum oxide.
4. The method of claim 3, wherein: the solid catalyst takes alumina as a carrier, and the alumina is gamma-AL 2O3 with hydroxyl on the surface and roasted at 800 +/-50 ℃.
5. The method of claim 3, wherein: the specific surface area of the solid catalyst is 400-500 square meters per gram, the bulk specific gravity is 0.45 +/-0.05 grams per milliliter, the acidity is + 3.2-3.5 Pka, and the granularity is 40-120 meshes.
6. The method of claim 1, wherein: the solid catalyst is composed of SiO2-AL2O3 or B2O3-AL2O3 as a carrier, zirconium oxide and tantalum oxide.
7. The method of claim 1, wherein: the specific surface area of the solid catalyst is 400-500 square meters per gram, the bulk specific gravity is 0.45 +/-0.05 grams per milliliter, the acidity is + 3.2-3.5 Pka, and the granularity is 40-120 meshes.
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| JP7262189B2 (en) * | 2018-08-03 | 2023-04-21 | 国立大学法人千葉大学 | Catalyst for producing conjugated diene, method for producing catalyst, and method for producing conjugated diene |
| CN110204411B (en) * | 2019-07-19 | 2021-04-06 | 中国科学院长春应用化学研究所 | Production system and method for synthesizing isoprene by olefine (ether) aldehyde gas phase method and comprehensively utilizing carbon deposition resistance, wastewater and waste heat |
| CN112645787B (en) * | 2019-10-11 | 2022-03-08 | 中国科学院大连化学物理研究所 | Method for preparing isoprene |
| CN114380658B (en) * | 2020-10-22 | 2023-04-11 | 中国科学院大连化学物理研究所 | Method for preparing isoprene by catalyzing isobutene-methanol with Pr-doped cerium oxide |
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| CN101024595A (en) * | 2006-02-24 | 2007-08-29 | 兰州红叶精细化工公司 | Process for cracking isobutene by methyl-tert-butyl ether |
| CN103467234A (en) * | 2013-09-04 | 2013-12-25 | 山东垦利石化集团有限公司 | Technology for synthesizing isoprene with olefine aldehyde |
| CN105130741A (en) * | 2015-10-13 | 2015-12-09 | 宁波金海晨光化学股份有限公司 | Method for preparing isoprene by means of reaction and distillation |
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| CN101024595A (en) * | 2006-02-24 | 2007-08-29 | 兰州红叶精细化工公司 | Process for cracking isobutene by methyl-tert-butyl ether |
| CN103467234A (en) * | 2013-09-04 | 2013-12-25 | 山东垦利石化集团有限公司 | Technology for synthesizing isoprene with olefine aldehyde |
| CN105130741A (en) * | 2015-10-13 | 2015-12-09 | 宁波金海晨光化学股份有限公司 | Method for preparing isoprene by means of reaction and distillation |
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