CN111943822A - Device and method for producing high-concentration formaldehyde by using methanol - Google Patents
Device and method for producing high-concentration formaldehyde by using methanol Download PDFInfo
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- CN111943822A CN111943822A CN202010998208.2A CN202010998208A CN111943822A CN 111943822 A CN111943822 A CN 111943822A CN 202010998208 A CN202010998208 A CN 202010998208A CN 111943822 A CN111943822 A CN 111943822A
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 288
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims abstract description 162
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 239000002250 absorbent Substances 0.000 claims abstract description 54
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- 239000007795 chemical reaction product Substances 0.000 claims abstract description 36
- 239000000047 product Substances 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 150000002373 hemiacetals Chemical class 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 238000004064 recycling Methods 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 13
- 238000010517 secondary reaction Methods 0.000 claims abstract description 12
- 238000007599 discharging Methods 0.000 claims abstract description 11
- 238000000926 separation method Methods 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims description 78
- 239000003054 catalyst Substances 0.000 claims description 51
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 30
- 238000010992 reflux Methods 0.000 claims description 24
- 238000003860 storage Methods 0.000 claims description 19
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 15
- 235000019253 formic acid Nutrition 0.000 claims description 15
- 238000012856 packing Methods 0.000 claims description 13
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- 230000003197 catalytic effect Effects 0.000 claims description 11
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical group O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 9
- 125000004122 cyclic group Chemical group 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 6
- HZNPCLUBXJLRAA-UHFFFAOYSA-N iron;oxomolybdenum Chemical compound [Fe].[Mo]=O HZNPCLUBXJLRAA-UHFFFAOYSA-N 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 239000011973 solid acid Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 2
- VSSAZBXXNIABDN-UHFFFAOYSA-N cyclohexylmethanol Chemical compound OCC1CCCCC1 VSSAZBXXNIABDN-UHFFFAOYSA-N 0.000 claims description 2
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- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical group C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- 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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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- 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
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C45/82—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- 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
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/85—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to a chemical modification
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Abstract
The invention discloses a device and a method for producing high-concentration formaldehyde by using methanol, which comprises a fan, a heat exchanger, a fixed bed reactor, an absorption tower, a refining tower and a pyrolysis tower which are connected in sequence; the method comprises the following steps of mixing air pressurized by a fan with a methanol raw material, flowing the mixture through a heat exchanger, then entering a fixed bed reactor for oxidation reaction, flowing a primary product through the heat exchanger, then entering an absorption tower for hemiacetal reaction, sequentially flowing a secondary reaction product through a refining tower and a pyrolysis tower for separation and pyrolysis, discharging an absorbent from the bottom of the tower for recycling after pyrolysis, and collecting a gaseous formaldehyde product obtained at the top of the tower. The product of the invention is dry gas formaldehyde which is quite stable, so the invention has obvious economic benefit and environmental protection advantage; the product of the invention has excellent quality: the concentration of formaldehyde is more than or equal to 99.9 percent, and the concentration of water is less than or equal to 0.05 percent.
Description
Technical Field
The invention relates to a device and a method for producing formaldehyde, in particular to a device and a method for producing formaldehyde by using methanol, and further relates to a device and a method for producing high-concentration formaldehyde by using methanol.
Background
Formaldehyde is an important organic chemical raw material, has wide application, is used in synthetic resin, surfactant, plastic, rubber, leather, papermaking, dye, pharmacy, pesticide, photographic film, explosive, building material and disinfection, fumigation and corrosion prevention processes, is a formaldehyde polymer series, a trioxadehyde glue series, a polyalcohol series, a heterocyclic compound series and the like, and is widely applied to various industries and fields of chemical industry and medicine production.
The formaldehyde belongs to a popular chemical product with wide application, simple production process and sufficient raw material supply, is the main stem of a downstream product tree of the methanol, the annual output of the world is about 2500 million tons, and about 30 percent of methanol is used for producing the formaldehyde. However, the formaldehyde commodity is usually an aqueous solution with a low concentration, and is inconvenient for long-distance transportation from the economic point of view, so that a factory is generally arranged near a main consumer market, and the import and export trade is also very little.
The boiling point of the formaldehyde is-19.5 ℃, the formaldehyde is gaseous at normal temperature and usually appears in the form of aqueous solution, the concentration of the aqueous solution can reach 55 percent at most, is usually 35-40 percent and is usually 37 percent, the aqueous solution is called formalin, the formalin is commonly called formalin and is easy to be turbid when being stored for a long time, and trioxymethylene precipitate is formed at low temperature. The formaldehyde can carry out condensation reaction, and 10% -12% of methanol is added as an inhibitor in common commercial products. Before formaldehyde is applied to downstream products, impurities such as water, methanol and the like in the formaldehyde aqueous solution need to be removed, so that extra large energy consumption is increased, and economic benefit reduction and environmental protection pressure are brought.
Disclosure of Invention
The invention aims to solve the technical problem of the prior art, and provides a device and a method for producing high-concentration formaldehyde by using methanol, wherein the device and the method take qualified industrial methanol (GB 338 plus 2011) or methanol and air with higher quality as raw materials, and are a technology for producing high-concentration formaldehyde by using methanol.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention firstly provides a device for producing high-concentration formaldehyde by using methanol, which comprises a fan, a heat exchanger, a fixed bed reactor, an absorption tower, a refining tower and a pyrolysis tower which are connected in sequence, and is characterized in that:
the fan, be equipped with feed inlet I and discharge gate I, wherein: the feed inlet I is divided into two paths, the first path is connected with a device capable of providing air, and the second path is connected with the absorption tower; the discharge port I is connected with the heat exchanger;
the heat exchanger, be equipped with cold material feed inlet II, hot material discharge gate II, hot material feed inlet III, cold material discharge gate III, wherein: the cold material feeding port II is divided into two paths, the first path is connected with the discharging port I of the fan, and the second path is connected with the methanol storage tank; the hot material discharge port II is connected with the fixed bed reactor; the hot material feed port III is connected with the fixed bed reactor; the cold material discharge port III is connected with the absorption tower;
fixed bed reactor, the top is equipped with feed inlet IV, the bottom is equipped with discharge gate IV, wherein: the feed inlet IV is connected with a hot material discharge outlet II of the heat exchanger; the discharge port IV is connected with a hot material feed port III of the heat exchanger;
absorption tower, the top is equipped with gas vent I, the bottom is equipped with discharge gate V, the upper portion that the middle part of tower wall one side was equipped with feed inlet V, tower wall opposite side is equipped with feed inlet VI, wherein: the feed inlet V is connected with a cold material discharge outlet III of the heat exchanger; the feeding port VI is divided into two paths, the first path is connected with the absorbent storage tank, and the second path is connected with the pyrolysis tower; the exhaust port I is divided into two paths, the first path is connected with the feed port I of the fan, and the second path is connected with the tail gas treatment device; the discharge port V is connected with the refining tower;
refining tower, the top be equipped with gas vent II, the bottom is equipped with discharge gate VI, the middle part of tower wall one side is equipped with feed inlet VII, the upper portion of tower wall opposite side is equipped with the backward flow mouth, wherein: the feed port VII is connected with a discharge port V of the absorption tower; the exhaust port II is sequentially connected with a condenser and a reflux tank, the outlet of the reflux tank is divided into two paths, the first path is connected with a reflux port, and the second path is connected with a methanol storage tank so as to recycle methanol; the discharge port VI is connected with the pyrolysis tower;
pyrolysis tower, the top be equipped with gas vent III, the bottom is equipped with discharge gate VII, the middle part of tower wall one side is equipped with feed inlet VIII, wherein: the feed inlet VIII is connected with a discharge outlet VI of the refining tower; the exhaust port III is connected with the product buffer tank; and the discharge port VII is connected with a feed port VI of the absorption tower so as to recycle the absorbent.
In the technical scheme, the fixed bed reactor is internally filled with a catalyst A; the catalyst A is iron molybdenum oxide.
In the technical scheme, the absorption tower is internally filled with a catalyst B; the catalyst B is a solid acid catalyst, preferably a macroporous sulfonic acid cation resin catalyst.
In the above-mentioned technical solution, the catalyst B is loaded in a combined structured packing form, and the structure of the combined structured packing is preferably a catalyst loaded combined structured packing structure described in patent CN204656548U (201520253109.6).
In the technical scheme, the fan, the heat exchanger, the fixed bed reactor, the absorption tower, the refining tower and the pyrolysis tower are all equipment or commercially available equipment in the prior art.
The invention firstly provides a method for producing high-concentration formaldehyde by using methanol, which comprises the following steps:
(1) and (3) oxidation reaction: after being pressurized by a fan, air is mixed with a methanol raw material and then sequentially flows through a cold material feeding port II, a hot material discharging port II and a feeding port IV and then is introduced into a fixed bed reactor, and the air and the methanol are subjected to oxidation reaction under the catalytic action of a catalyst A in the fixed bed reactor to obtain a primary reaction product, wherein the primary product is formaldehyde, trace formic acid and water, and unreacted methanol and air; the primary reaction product sequentially flows through a discharge port IV, a hot material feed port III, a cold material discharge port III and a feed port V, and enters the absorption tower after heat exchange by a heat exchanger;
(2) hemiacetalization reaction: the primary reaction product formed in the fixed bed reactor enters an absorption tower, meanwhile, an absorbent also enters the absorption tower from a feed inlet VI, and the primary product and the absorbent are subjected to hemiacetal reaction under the catalytic action of a catalyst B in the tower and are separated; after separation, light components are obtained at the top of the tower, the light components comprise unreacted air, trace methanol, formaldehyde and an absorbent, one part of the light components is discharged from the exhaust port I and then returned to the fan from the feed port I for recycling, and the other part of the light components is connected with a tail gas treatment device; a secondary reaction product is obtained at the bottom of the tower after separation, the secondary reaction product is a mixture of hemiacetal obtained by reacting formaldehyde with an absorbent, the remaining absorbent, a small amount of methanol, formic acid and a small amount of water, and the mixture sequentially flows through a discharge hole V and a feed hole VII and then enters a refining tower;
(3) refining: the second-stage reaction product at the bottom of the absorption tower enters a refining tower, is separated in the refining tower, and light components are obtained at the top of the tower, are gaseous methanol, formic acid, water and trace heavy components, are discharged from an exhaust port II and are condensed into liquid through a condenser to enter a reflux tank, one part of the material in the reflux tank returns to the refining tower through a reflux port for recycling, and the other part of the material returns to a methanol storage tank for recycling; the separated heavy components comprise hemiacetal obtained by the reaction of methanol and the absorbent and the remaining absorbent, and the hemiacetal and the remaining absorbent sequentially flow through a discharge port VI and a feed port VIII and then enter the pyrolysis tower;
(4) pyrolysis: after the heavy component at the bottom of the refining tower enters a pyrolysis tower, carrying out pyrolysis in the pyrolysis tower to obtain a light component at the top of the tower, wherein the light component is gaseous formaldehyde and is connected with a formaldehyde product buffer tank after being discharged from an exhaust port III; and the material discharged from a discharge port VII at the bottom of the tower is an absorbent and returns to an absorbent storage tank for recycling.
In the technical scheme, in the step (1), a primary product is obtained along with the oxidation reaction, the temperature of the primary product is relatively high and is equivalent to that of a hot material, and the temperature of air and methanol is relatively low and is equivalent to that of a cold material; air and methanol sequentially flow through a cold material feeding hole II and a hot material discharging hole II of the heat exchanger, primary products sequentially flow through a hot material feeding hole III and a cold material discharging hole III of the heat exchanger, and cold and hot materials exchange heat in the heat exchanger; the methanol is heated into vaporized methanol after heat exchange and then enters the fixed bed reactor together with air for reaction, and the primary product is cooled after heat exchange and then enters the absorption tower.
In the above technical scheme, in the step (1), the methanol raw material is qualified product or higher grade methanol meeting the requirements of industrial methanol GB 338-.
In the technical scheme, in the step (1), the air is pressurized to 0.20-0.40 Mpa by a fan.
In the technical scheme, in the step (1), the volume ratio of the vaporized methanol to the air is 3-8: 100, preferably 5.5-6.5: 100.
in the technical scheme, in the step (1), the volume airspeed of vaporized methanol and air which are introduced into the fixed bed reactor together is 2-10 h-1。
In the technical scheme, in the step (1), the reaction temperature in the fixed bed reactor is 300-360 ℃, preferably 345-355 ℃, and the reaction pressure is 0.15-0.25 Mpa.
In the technical scheme, in the step (1), the catalyst A is iron-molybdenum oxide comprising iron molybdate and molybdenum trioxide, and the molar ratio of molybdenum to iron is 1.8-3.3: 1.
in the technical scheme, in the step (2), the primary reaction product formed in the fixed bed reactor enters the absorption tower at a volume space velocity of 1-6 h-1。
In the above technical scheme, in the step (2), the catalyst B is a solid acid catalyst, preferably a macroporous sulfonic acid cationic resin catalyst.
In the above technical scheme, in the step (2), the hemiacetal reaction is performed under the following reaction conditions: the reaction temperature is 70-100 ℃, and the reaction pressure is 0.10-0.20 Mpa.
In the above technical solution, in the step (2), the operation conditions of the absorption tower are as follows: the temperature at the top of the tower is 70-100 ℃, and the pressure is 0.10-0.15 Mpa; the temperature of the tower bottom is 70-100 ℃, and the pressure is 0.10-0.25 Mpa.
In the technical scheme, in the step (2), in the process of absorption in the absorption tower, excessive absorbent is introduced from the feed inlet VI, so that the reaction is favorably carried out in the direction of absorbing formaldehyde; the mol ratio of the absorbent to the methanol is 1-2: 1, preferably 1.1 to 1.3: 1.
in the above technical scheme, in the step (2), the absorbent is a mixture of any one, two or more of n-heptanol, benzyl alcohol, cyclohexylmethanol and other alcohols with a boiling point of 160-210 ℃ mixed at any ratio.
In the above technical solution, in the step (3), the refining tower has the following operating conditions: the temperature at the top of the column is 75 to 105 ℃, the pressure is 0.05 to 0.10MPa, the temperature at the bottom of the column is 95 to 115 ℃, and the pressure is 0.10 to 0.15 MPa.
In the above technical solution, in the step (4), the operation conditions of the pyrolysis tower are as follows: the temperature at the top of the tower is 140-150 ℃, the pressure is 0.10-0.15 Mpa, the temperature at the bottom of the tower is 140-150 ℃, and the pressure is 0.10-0.25 Mpa.
The technical scheme of the invention has the advantages that:
(1) the product of the invention has excellent quality: the concentration of formaldehyde is more than or equal to 99.9 percent, and the concentration of water is less than or equal to 0.05 percent.
(2) The special property of formaldehyde is that the formaldehyde is easy to polymerize, usually appears in the form of aqueous solution, contains 10% -12% of methanol as an inhibitor, and is required to prepare pure formaldehyde before being applied to downstream products, so that a large amount of wastewater and byproduct methanol are generated, and a large amount of energy consumption is additionally increased.
Drawings
FIG. 1: the overall structure of the device is schematic;
FIG. 2: a process flow diagram of the method of the invention;
wherein: 1 is a fan, 2 is a heat exchanger, 3 is a fixed bed reactor, 4 is an absorption tower, 5 is a refining tower, and 6 is a pyrolysis tower.
Detailed Description
The following detailed description of the embodiments of the present invention is provided, but the present invention is not limited to the following descriptions:
the invention firstly provides a device for producing high-concentration formaldehyde by using methanol, which comprises a fan 1, a heat exchanger 2, a fixed bed reactor 3, an absorption tower 4, a refining tower 5 and a pyrolysis tower 6 which are connected in sequence, as shown in figure 1:
In the invention, the fixed bed reactor 3 is internally filled with a catalyst A; the catalyst A is iron molybdenum oxide.
In the present invention, the absorption tower 4 is filled with a catalyst B; the catalyst B is a solid acid catalyst, preferably a macroporous sulfonic acid cation resin catalyst.
In the present invention, the catalyst B is packed in a combined structured packing, and the structure of the combined structured packing is preferably a catalyst-packed combined structured packing structure described in patent CN204656548U (201520253109.6).
In the invention, the fan, the heat exchanger, the fixed bed reactor, the absorption tower, the refining tower and the pyrolysis tower are all equipment in the prior art or commercially available equipment.
The invention firstly provides a method for producing high-concentration formaldehyde by using methanol, a flow chart is shown in figure 2, and the method comprises the following steps:
(1) and (3) oxidation reaction: after being pressurized by a fan 1, air is mixed with a methanol raw material and then flows through a cold material feeding port II, a hot material discharging port II and a feeding port IV in sequence and then is introduced into a fixed bed reactor 3, the air and the methanol are subjected to oxidation reaction under the catalytic action of a catalyst A in the fixed bed reactor 3 to obtain a primary reaction product, and the primary reaction product comprises formaldehyde, trace formic acid, water, unreacted methanol and air; the primary reaction product sequentially flows through a discharge port IV, a hot material feed port III, a cold material discharge port III and a feed port V, exchanges heat through a heat exchanger 2 and then enters an absorption tower 4;
(2) hemiacetalization reaction: the primary reaction product formed in the fixed bed reactor 3 enters an absorption tower 4, meanwhile, an absorbent also enters the absorption tower from a feed inlet VI, and the primary product and the absorbent are subjected to a hemiacetal reaction under the catalytic action of a catalyst B in the tower and are separated; after separation, light components are obtained at the top of the tower, the light components comprise unreacted air, trace methanol, formaldehyde and an absorbent, one part of the light components is discharged from the exhaust port I and then returned to the fan 1 from the feed port I for recycling, and the other part of the light components is connected with a tail gas treatment device; a secondary reaction product is obtained at the bottom of the tower after separation, the secondary reaction product is a mixture of hemiacetal obtained by reacting formaldehyde with an absorbent, the remaining absorbent, a small amount of methanol, formic acid and a small amount of water, and the mixture sequentially flows through a discharge hole V and a feed hole VII and then enters a refining tower 5;
(3) refining: the secondary reaction product at the bottom of the absorption tower (4) enters a refining tower 5, is separated in the refining tower 5, and light components are obtained at the top of the tower, are gaseous methanol, formic acid, water and trace heavy components, are discharged from an exhaust port II and are condensed into liquid through a condenser to enter a reflux tank, one part of the material in the reflux tank returns to the refining tower 5 through a reflux port for recycling, and the other part of the material returns to a methanol storage tank for recycling; the separated heavy components comprise hemiacetal obtained by the reaction of methanol and the absorbent and the remaining absorbent, and the hemiacetal and the remaining absorbent sequentially flow through a discharge port VI and a feed port VIII and then enter a pyrolysis tower 6;
(4) pyrolysis: after the heavy component at the bottom of the refining tower 5 enters the pyrolysis tower 6, pyrolyzing the heavy component in the pyrolysis tower 6 to obtain a light component at the top of the tower, wherein the light component is gaseous formaldehyde and is connected with a formaldehyde product buffer tank after being discharged from an exhaust port III; and the material discharged from a discharge port VII at the bottom of the tower is an absorbent and returns to an absorbent storage tank for recycling.
The invention will now be illustrated with reference to specific examples:
example 1:
a method for producing high-concentration formaldehyde by using methanol specifically comprises the following steps:
(1) and (3) oxidation reaction: after air is pressurized by a fan 1, qualified products of industrial methanol (GB 338-:100 flows through the heat exchanger 2 after being mixed and then flows through a feed inlet IV (the volume space velocity is 5 h)-1) Introducing the mixture into a fixed bed reactor 3, and carrying out oxidation reaction on air and methanol under the catalysis of a catalyst A (comprising iron molybdate and molybdenum trioxide, wherein the molar ratio of molybdenum to iron is 3:1) in the fixed bed reactor 3, wherein the reaction temperature is 345-350 ℃, and the reaction pressure is 0.18-0.20 Mpa, so as to obtain a primary reaction product; the primary reaction product is a mixture of formaldehyde, unreacted methanol, formic acid, and water. The primary reaction product flows through a discharge port IV and a feed port III in sequence, enters a heat exchanger 2 for heat exchange, and then enters an absorption tower 4;
(2) hemiacetalization reaction: the primary reaction product formed in the fixed bed reactor 3 enters the absorption tower 4 (the volume space velocity is 4 h)-1) Reacting with absorbent benzyl alcohol under the catalysis of catalyst B (catalyst B is KC107 type catalyst of Kery environmental protection science and technology Co., Ltd.) in the tower, and separating; the molar ratio of benzyl alcohol to methanol was 1.2: 1. after separation, light components are obtained at the top of the tower, the light components comprise unreacted air, trace methanol, formaldehyde, absorbent and the like, one part of the light components is discharged from the exhaust port I and then returns to the fan 1 from the feed port I for recycling, and the other part of the light components is connected with a tail gas treatment device; separating to obtain a secondary reaction product at the bottom of the tower, wherein the secondary reaction product is a mixture of hemiacetal obtained by the reaction of formaldehyde and benzyl alcohol, a residual absorbent, a small amount of methanol, trace water and formic acid, and the mixture sequentially flows through a discharge hole V and a feed hole VII and then enters a refining tower 5; the operating conditions of the absorption column 4 were: the temperature at the top of the column was 80 ℃ and the pressure 0.12MPa, and the temperature at the bottom of the column was 85 ℃ and the pressure 0.14 MPa.
In this example, the loading form of the catalyst refers to the combined structured packing of the loaded catalyst in patent CN204656548U (201520253109.6), which includes: a plurality of catalyst mould sheets filled with catalyst particles, a plurality of metal pore plate corrugated packing sheets 2 and a bundle type steel belt; the catalyst matrix is formed by pressing a metal diamond plate lined with a metal wire mesh made of the same material into a specified shape, and then filling catalyst particles into the metal diamond plate for spot welding and sealing; the shape of the catalyst particles can be varied, and the catalyst particles given in this example are spherical particles having a diameter of 0.355 to 1.25 mm; the catalyst matrix is formed by spot welding and compounding a 4 x 8 stainless steel diamond plate mesh and a 60-mesh stainless steel wire mesh made of the same material and then pressing the mixture into two isosceles trapezoid structures with the cross sections having bottom angles not less than 60 degrees, and the two ends of the isosceles trapezoid structures are sealed; the metal orifice plate packing sheet is 150-type 700X or 150-type 700Y, and the 700Y-type stainless steel orifice plate corrugated packing sheet is selected in the embodiment; a plurality of catalyst matrixes and stainless steel orifice plate ripple packing pieces 2 are bundled by the same material steel band after being arranged in a linear equidistant staggered mode along the diameter direction of the tower, and finally, the wall flow preventing ring is installed, so that the stability and the catalytic distillation effect of the catalytic distillation element are further ensured, and meanwhile, the catalytic distillation element is more convenient to enter the tower for installation.
(3) Refining: the second-order reaction product at the bottom of the absorption tower enters a refining tower 5 and is separated in the refining tower 5 under the following operation conditions: the temperature at the top of the column was 95 ℃ and the pressure 0.06MPa, and the temperature at the bottom of the column was 105 ℃ and the pressure 0.11 MPa. Obtaining light components at the top of the tower, wherein the light components comprise gaseous methanol, formic acid, water and trace heavy components, are discharged from an exhaust port II and condensed into liquid through a condenser to enter a reflux tank, one part of materials in the reflux tank returns to the refining tower 5 through a reflux port for cyclic utilization, and the other part of materials returns to a methanol storage tank for cyclic utilization; heavy substances discharged from a discharge hole VI at the bottom of the tower are hemiacetal generated by the reaction of methanol and benzyl alcohol and residual absorbent;
(4) pyrolysis: after the material hemiacetal at the bottom of the refining tower 5 enters a pyrolysis tower 6, pyrolyzing the material hemiacetal in the pyrolysis tower to obtain a light component at the top of the tower, wherein the light component is gaseous formaldehyde and is connected with a formaldehyde product buffer tank; the material discharged from a discharge port VII at the bottom of the tower is an absorbent and returns to an absorbent storage tank for recycling; the operating conditions of the pyrolysis tower are as follows: the temperature at the top of the column was 145 ℃ and the pressure was 0.12MPa, and the temperature at the bottom of the column was 145 ℃ and the pressure was 0.12 MPa.
In the product of this example, the concentration of formaldehyde was 99.92% and the concentration of water was 0.04%.
Example 2:
a method for producing high-concentration formaldehyde by using methanol specifically comprises the following steps:
(1) and (3) oxidation reaction: after air is pressurized by a fan 1, the air and qualified products of industrial methanol (GB 338-The product ratio is 5.5: 100, flows through a heat exchanger 2 and then passes through a feed inlet IV (the volume space velocity is 5 h)-1) Introducing the mixture into a fixed bed reactor 3, and carrying out oxidation reaction on air and methanol under the catalytic action of a catalyst A (the same as that in the example 1) in the fixed bed reactor at the reaction temperature of 345-350 ℃ and the reaction pressure of 0.18-0.20 Mpa to obtain a primary reaction product; the primary reaction product is a mixture of formaldehyde, unreacted methanol, formic acid, and water. The primary reaction product flows through a discharge port IV and a feed port III in sequence, enters a heat exchanger 2 for heat exchange, and then enters an absorption tower 4;
(2) hemiacetalization reaction: the primary reaction product formed in the fixed bed reactor 3 enters the absorption tower 4 (space velocity of 4 h)-1) And n-heptanol as an absorbent are subjected to hemiacetal reaction under the catalytic action of a catalyst B (the arrangement of the catalyst B and the combined regular packing is the same as that in the example 1) in the tower and are separated; the molar ratio of n-heptanol to methanol was 1.15: 1. after separation, light components are obtained at the top of the tower, the light components comprise unreacted air, trace methanol, formaldehyde, absorbent and the like, one part of the light components is discharged from the exhaust port I and then returns to the fan 1 from the feed port I for recycling, and the other part of the light components is connected with a tail gas treatment device; separating to obtain a secondary reaction product at the bottom of the tower, wherein the secondary reaction product is a mixture of hemiacetal obtained by reacting formaldehyde with n-heptanol, a residual absorbent, a small amount of methanol, a trace amount of water and formic acid, and the mixture sequentially flows through a discharge hole V and a feed hole VII and then enters a refining tower 5; the operating conditions of the absorption column 4 were: the temperature at the top of the column was 83 ℃ and the pressure 0.13MPa, and the temperature at the bottom of the column was 87 ℃ and the pressure 0.15 MPa.
(3) Refining: the second-stage reaction product at the bottom of the absorption tower 4 enters a refining tower 5, and is separated in the refining tower under the following operating conditions: the temperature at the top of the column was 97 ℃ and the pressure was 0.06MPa, and the temperature at the bottom of the column was 108 ℃ and the pressure was 0.11 MPa. Obtaining light components at the tower top, wherein the light components are gaseous methanol, formic acid, water and trace heavy components, are discharged from an exhaust port II and condensed into liquid through a condenser to enter a reflux tank, one part of materials in the reflux tank returns to the refining tower through a reflux port for cyclic utilization, and the other part of materials returns to a methanol storage tank for cyclic utilization; heavy substances discharged from a discharge hole VI at the bottom of the tower are hemiacetal and residual absorbent generated by the reaction of methanol and n-heptanol;
(4) pyrolysis: after the material hemiacetal at the bottom of the refining tower 5 enters a pyrolysis tower 6, pyrolyzing the material hemiacetal in the pyrolysis tower to obtain a light component at the top of the tower, wherein the light component is gaseous formaldehyde and is connected with a formaldehyde product buffer tank; materials discharged from a discharge port VII at the bottom of the tower are mainly absorbent and return to an absorbent storage tank for recycling; the operating conditions of the pyrolysis tower are as follows: the temperature at the top of the column was 147 ℃ and the pressure was 0.13MPa, and the temperature at the bottom of the column was 147 ℃ and the pressure was 0.13 MPa.
In the product of this example, the concentration of formaldehyde was 99.94% and the concentration of water was 0.03%.
The above examples are only for illustrating the technical concept and features of the present invention, and are not intended to limit the scope of the present invention. All equivalent changes or modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (10)
1. A method for producing high-concentration formaldehyde by using methanol is characterized by comprising the following steps:
(1) and (3) oxidation reaction: after being pressurized by a fan (1), air is mixed with a methanol raw material and then flows through a cold material feeding port II, a hot material discharging port II and a feeding port IV in sequence and then is introduced into a fixed bed reactor (3), the air and the methanol are subjected to oxidation reaction under the catalytic action of a catalyst A in the fixed bed reactor (3) to obtain a primary reaction product, and the primary product is formaldehyde, trace formic acid and water, unreacted methanol and air; the primary reaction product sequentially flows through a discharge port IV, a hot material feed port III, a cold material discharge port III and a feed port V, exchanges heat through a heat exchanger (2) and then enters an absorption tower (4);
(2) hemiacetalization reaction: the primary reaction product formed in the fixed bed reactor (3) enters an absorption tower (4), meanwhile, an absorbent also enters the absorption tower from a feed inlet VI, and the primary product and the absorbent are subjected to hemiacetal reaction under the catalytic action of a catalyst B in the tower and are separated; after separation, light components are obtained at the top of the tower, the light components comprise unreacted air, trace methanol, formaldehyde and an absorbent, one part of the light components is discharged from the exhaust port I and then returns to the fan (1) from the feed port I for recycling, and the other part of the light components is connected with a tail gas treatment device; a secondary reaction product is obtained at the bottom of the tower after separation, the secondary reaction product is a mixture of hemiacetal obtained by the reaction of formaldehyde and an absorbent, the remaining absorbent, a small amount of methanol, formic acid and a small amount of water, and the mixture sequentially flows through a discharge hole V and a feed hole VII and then enters a refining tower (5);
(3) refining: the second-stage reaction product at the bottom of the absorption tower (4) enters a refining tower (5), is separated in the refining tower (5), light components are obtained at the top of the tower, are gaseous methanol, formic acid, water and trace heavy components, are discharged from an exhaust port II and are condensed into liquid through a condenser, and enter a reflux tank, one part of the material in the reflux tank returns to the refining tower (5) through a reflux port for cyclic utilization, and the other part returns to a methanol storage tank for cyclic utilization; the separated heavy components comprise hemiacetal obtained by the reaction of methanol and the absorbent and the remaining absorbent, and the hemiacetal and the remaining absorbent flow through a discharge port VI and a feed port VIII in sequence and then enter a pyrolysis tower (6);
(4) pyrolysis: after the heavy component at the bottom of the refining tower (5) enters the pyrolysis tower (6), pyrolyzing the heavy component in the pyrolysis tower (6) to obtain a light component at the top of the tower, wherein the light component is gaseous formaldehyde and is connected with a formaldehyde product buffer tank after being discharged from an exhaust port III; and the material discharged from a discharge port VII at the bottom of the tower is an absorbent and returns to an absorbent storage tank for recycling.
2. The method of claim 1, wherein in step (1), as the oxidation reaction proceeds, a primary product is obtained, which has a relatively high temperature corresponding to a hot feed, and air and methanol have a relatively low temperature corresponding to a cold feed; air and methanol sequentially flow through a cold material feeding hole II and a hot material discharging hole II of the heat exchanger, primary products sequentially flow through a hot material feeding hole III and a cold material discharging hole III of the heat exchanger, and cold and hot materials exchange heat in the heat exchanger; the methanol is heated into vaporized methanol after heat exchange and then enters the fixed bed reactor together with air for reaction, and the primary product is cooled after heat exchange and then enters the absorption tower (4).
3. The method as claimed in claim 1, wherein in step (1), the methanol raw material is qualified methanol or higher grade methanol meeting the industrial methanol GB 338-2011 requirements; pressurizing the air to 0.20-0.40 Mpa by a fan; the catalyst A is an iron-molybdenum oxide and comprises iron molybdate and molybdenum trioxide, and the molar ratio of molybdenum to iron is 1.8-3.3: 1.
4. the method according to claim 1 or 2, wherein in the step (1), the volume ratio of the vaporized methanol to the air is 3-8: 100, respectively; the volume space velocity of the vaporized methanol and the air which are introduced into the fixed bed reactor (3) is 2-10 h-1。
5. The method according to claim 1, wherein in the step (1), the reaction temperature in the fixed bed reactor (3) is 300-360 ℃, and the reaction pressure is 0.15-0.25 MPa.
6. The method according to claim 1, wherein in the step (2), the volume space velocity of the primary reaction product formed in the fixed bed reactor (3) entering the absorption tower (4) is 1-6 h-1(ii) a The catalyst B is a solid acid catalyst; the absorbent is a mixture formed by mixing any one, two or more than two of n-heptanol, benzyl alcohol, cyclohexylmethanol and other alcohols with the boiling point of 160-210 ℃; the mol ratio of the absorbent to the methanol is 1-2: 1.
7. the process according to claim 1, wherein in step (2), the hemiacetal is reacted under the following reaction conditions: the reaction temperature is 70-100 ℃, and the reaction pressure is 0.10-0.20 Mpa; the operation conditions of the absorption tower (4) are as follows: the temperature at the top of the tower is 70-100 ℃, and the pressure is 0.10-0.15 Mpa; the temperature of the tower bottom is 70-100 ℃, and the pressure is 0.10-0.25 Mpa.
8. The method according to claim 1, wherein in the step (3), the refining column (5) is operated under the following conditions: the temperature at the top of the tower is 75-105 ℃, the pressure is 0.05-0.10 Mpa, the temperature at the bottom of the tower is 95-115 ℃, and the pressure is 0.10-0.15 Mpa; in the step (4), the operation conditions of the pyrolysis tower (6) are as follows: the temperature at the top of the tower is 140-150 ℃, the pressure is 0.10-0.15 Mpa, the temperature at the bottom of the tower is 140-150 ℃, and the pressure is 0.10-0.25 Mpa.
9. The utility model provides an utilize device of methyl alcohol production high concentration formaldehyde, includes fan (1), heat exchanger (2), fixed bed reactor (3), absorption tower (4) that connect gradually, refining tower (5), pyrolysis tower (6), its characterized in that:
fan (1), be equipped with feed inlet I and discharge gate I, wherein: the feed inlet I is divided into two paths, the first path is connected with a device capable of providing air, and the second path is connected with the absorption tower (4); the discharge port I is connected with the heat exchanger (2);
heat exchanger (2), be equipped with cold material feed inlet II, hot material discharge gate II, hot material feed inlet III, cold material discharge gate III, wherein: the cold material feeding port II is divided into two paths, the first path is connected with the discharging port I of the fan (1), and the second path is connected with the methanol storage tank; the hot material discharge port II is connected with the fixed bed reactor (3); the hot material feed port III is connected with the fixed bed reactor (3); the cold material discharge port III is connected with the absorption tower (4);
fixed bed reactor (3), the top is equipped with feed inlet IV, the bottom is equipped with discharge gate IV, wherein: the feed inlet IV is connected with a hot material discharge outlet II of the heat exchanger (2); the discharge port IV is connected with a hot material feed port III of the heat exchanger (2);
absorption tower (4), the top is equipped with gas vent I, the bottom is equipped with discharge gate V, the upper portion that the middle part of tower wall one side was equipped with feed inlet V, tower wall opposite side is equipped with feed inlet VI, wherein: the feed inlet V is connected with a cold material discharge outlet III of the heat exchanger (2); the feeding port VI is divided into two paths, the first path is connected with the absorbent storage tank, and the second path is connected with the pyrolysis tower (6); the exhaust port I is divided into two paths, the first path is connected with a feed port I of the fan (1), and the second path is connected with a tail gas treatment device; the discharge port V is connected with a refining tower (5);
refining tower (5), the top is equipped with gas vent II, the bottom is equipped with discharge gate VI, the middle part of tower wall one side is equipped with feed inlet VII, the upper portion of tower wall opposite side is equipped with the backward flow mouth, wherein: the feed port VII is connected with a discharge port V of the absorption tower (4); the exhaust port II is sequentially connected with a condenser and a reflux tank, the outlet of the reflux tank is divided into two paths, the first path is connected with a reflux port, and the second path is connected with a methanol storage tank so as to recycle methanol; the discharge port VI is connected with the pyrolysis tower (6);
pyrolysis tower (6), the top is equipped with gas vent III, the bottom is equipped with discharge gate VII, the middle part of tower wall one side is equipped with feed inlet VIII, wherein: the feed inlet VIII is connected with a discharge outlet VI of the refining tower (5); the exhaust port III is connected with the product buffer tank; the discharge port VII is connected with the feed port VI of the absorption tower (4) so as to recycle the absorbent.
10. The apparatus of claim 9, wherein: the fixed bed reactor (3) is internally filled with a catalyst A; the catalyst A is iron-molybdenum oxide; the absorption tower (4) is internally filled with a catalyst B; the catalyst B is a solid acid catalyst; the filling form of the catalyst B is a combined regular packing form.
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