CN110790646A - Production process for preparing formaldehyde by oxidizing methanol with iron-molybdenum method - Google Patents

Production process for preparing formaldehyde by oxidizing methanol with iron-molybdenum method Download PDF

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Publication number
CN110790646A
CN110790646A CN201910865069.3A CN201910865069A CN110790646A CN 110790646 A CN110790646 A CN 110790646A CN 201910865069 A CN201910865069 A CN 201910865069A CN 110790646 A CN110790646 A CN 110790646A
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gas
methanol
iron
formaldehyde
waste gas
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张雄斌
关刚
章小林
邓建康
罗平
曹新峰
李国炜
李程明
单芙蓉
蒋吉峻
王登新
李新怀
李小定
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XINJIANG TIANZHI CHENYE CHEMICAL Co Ltd
HUASHUO TECHNOLOGY Co Ltd
Xinjiang Tianye Group Co Ltd
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XINJIANG TIANZHI CHENYE CHEMICAL Co Ltd
HUASHUO TECHNOLOGY Co Ltd
Xinjiang Tianye Group Co Ltd
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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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  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

The invention provides a production process for preparing formaldehyde by oxidizing methanol by an iron-molybdenum method. The process uses a catalyst containing N2Waste gas of O or containing N2The mixed gas of the waste gas of O and air is used as an oxidant, and methanol is oxidized by an iron-molybdenum method to prepare formaldehyde. The invention provides a method for preparing formaldehyde by oxidizing methanol with iron and molybdenum, which can realize the use of N-containing2Waste gas of O or containing N2The mixture of O waste gas and air as oxidant to prepare formaldehyde can reduce N2O is discharged, so that the resource utilization of waste is realized, and the environmental pollution is reduced; the explosion danger of the methanol in the raw material gas is reduced, the content of the methanol at the inlet is effectively improved, the productivity of the device is improved, the yield of the product formaldehyde is improved, and the economic and social benefits of enterprises are increased; the domestic iron-molybdenum catalyst can also achieve excellent catalytic effect and break the monopoly abroad.

Description

Production process for preparing formaldehyde by oxidizing methanol with iron-molybdenum method
Technical Field
The invention relates to the production field of formaldehyde by oxidizing methanol by an iron-molybdenum method, in particular to a production process for preparing formaldehyde by oxidizing methanol by an iron-molybdenum method.
Background
The iron-molybdenum method is an important process for preparing formaldehyde by methanol oxidation. Compared with the traditional silver method process, the iron-molybdenum method formaldehyde has the characteristics of high concentration, low methanol content and the like, and is high-quality formaldehyde. Therefore, in order to meet the requirements of high-concentration and high-quality formaldehyde in recent years, the process flows of 1, 4-butanediol, MDI, paraformaldehyde, polyformaldehyde and the like are generally matched with the process for preparing formaldehyde by methanol oxidation by an iron-molybdenum method.
The process flow mainly comprises the following steps: fresh air enters a booster fan through a silencer and an air filter to be boosted, air at an air outlet of the fan and circulating tail gas at the top of an absorption tower are mixed and enter a No. 1 circulating fan, then enter the No. 1 circulating fan to be continuously pressurized to a certain operating pressure and then are sent to a methanol evaporator to be mixed with methanol, and the methanol absorbs heat and is vaporized to form raw material gas. Raw material gas enters a main reactor, oxidation reaction is carried out on iron-molybdenum catalyst to generate formaldehyde reaction gas, and the formaldehyde reaction gas enters an absorption tower after being cooled. Most of formaldehyde in the absorption tower is absorbed, most of residual gas is sent by a circulating fan to be mixed with fresh air, and a small part of residual gas enters an ECS system and is discharged into the atmosphere after catalytic combustion.
The process adopts air as an oxidant, and because methanol and air are mixed to form explosive gas, the content of the methanol in raw material gas cannot be more than 6.67 percent due to the limitation of explosion limit, a tail gas circulation technology is developed in foreign countries in the year, part of tail gas is circularly added into fresh air, and the explosion limit range is reduced by reducing the oxygen content of the raw material gas, so that the content of the methanol in the raw material gas at the inlet is improved, but the content can be improved to about 10 percent at most, so that the production capacity of a single pipe is limited, and the improvement of the capacity of the whole device is influenced.
In addition, a large amount of N is emitted during the production of adipic acid2O, N in adipic acid tail gas is reported2The volume fraction of O is up to 35%, and N is2The emission of O occupies N worldwide210% of the total O emission. During the ammoxidation stage of the nitric acid production process, N is produced2O, which is difficult to remove in the subsequent process production, is estimated to be N discharged from the global nitric acid plant every year2O up to 400,000t, is to produce N2The largest source of O. For a nitric acid plant producing 1500 tons per day, the exhaust gas flow is 200,000Nm3，N2The content of O is as high as 1500ppmv, and the emission-limiting potential is huge. As is well known, N2O is a main greenhouse gas and has serious damage effect on the ozone layer, and N is generally considered to be the contribution degree of the current atmospheric greenhouse gas component to global warming2O is second to CO only2And CH4. However, due to N2O has an average life of 120 years in the troposphere, is extremely stable, and has a greenhouse effect of CH421 times of that of, CO2310 times higher. With the increasing awareness of environmental protection, and environmental regulationsThe more stringent the requirements, for N2It is important to perform harmless treatment on O. The most common method at present is to react N with the aid of a catalyst2O decomposition of N2、O2Although the purpose of emission reduction can be achieved, only N is used2And the waste is treated, so that the resources are wasted.
The adipic acid tail gas components are shown in the following table:
Figure BDA0002201018810000011
Figure BDA0002201018810000021
disclosure of Invention
The invention aims to provide a production process for preparing formaldehyde by methanol oxidation by an iron-molybdenum method.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
a process for preparing formaldehyde by oxidizing methanol with Fe-Mo method features use of N-contained catalyst2Waste gas of O or containing N2The mixed gas of the waste gas of O and air is used as an oxidant, and methanol is oxidized by an iron-molybdenum method to prepare formaldehyde.
According to the scheme, the N is contained2The waste gas of O is tail gas generated in the production process of adipic acid, and N discharged in the caprolactam or nitric acid industry2And (4) O waste gas.
According to the scheme, the N is contained2Waste gas of O or containing N2In the mixed gas of the waste gas of O and air and the raw material gas of methanol, N is calculated by volume percentage2Conversion of O to O2Metering (2 molecules N)2O is equivalent to 1 molecule of O2)，(O2+N2O) content of 11-20%, wherein N2The content of O is 8 to 15 percent, and O2The content is 3% -8%.
According to the scheme, the content of N is controlled2Waste gas of O or containing N2The flow ratio of the mixed gas of the waste gas of O and air to the methanol gas is 1: 1-1: 5, preferably 1: 2.
According to the scheme, the catalyst comprisesN2Waste gas of O or containing N2The content of methanol in the mixed gas of the waste gas of O and air and the raw material gas of methanol is 10 to 18 percent.
According to the scheme, the iron-molybdenum catalyst for preparing formaldehyde by oxidizing methanol by using an iron-molybdenum method is an EQ-101 type domestic formaldehyde catalyst which is the first creation of Hua Xuan science and technology GmbH in China.
According to the scheme, the temperature range of the iron-molybdenum method catalysis is 280-330 ℃.
According to the scheme, tail gas generated in the process is used as circulating tail gas and contains N2Waste gas of O or containing N2Mixing the waste gas of O with the mixed gas of air to prepare raw material gas, and oxidizing methanol by an iron-molybdenum method to prepare formaldehyde.
According to the scheme, the production process for preparing formaldehyde by methanol oxidation by the iron-molybdenum method comprises the following steps:
1) providing a compound containing N2Waste gas of O or containing N2The mixed gas of the waste gas of the O and the air enters a booster fan to be boosted;
2) boosting the pressure of the booster fan and mixing the boosted pressure with the methanol;
3) the raw material gas containing methanol with certain concentration is formed after heat absorption and vaporization in the evaporator;
4) and the raw material gas enters a main reactor and is subjected to oxidation reaction under the catalysis of an iron-molybdenum catalyst to generate formaldehyde reaction gas, and the formaldehyde reaction gas enters an absorption tower after being cooled and is absorbed by the absorption tower to obtain the product formaldehyde.
According to the scheme, fresh air containing N is mixed2Preparing the waste gas of O to obtain (O)2+2N2O) mixed gas with certain content; the residual gas not absorbed by the absorption tower can be mixed with fresh air according to the requirement and contains N2Preparing the waste gas of O to obtain (O)2+2N2O) mixed gas with certain content.
The invention has the beneficial effects that:
the invention provides a method for preparing formaldehyde by oxidizing methanol with iron and molybdenum, which can realize the use of N-containing2Waste gas of O or containing N2The mixture of O waste gas and air as oxidant to prepare formaldehyde can reduce N2O is discharged, so that the resource utilization of waste is realized, and the environmental pollution is reduced;
the explosion danger of the methanol in the raw material gas is reduced, the content of the methanol at the inlet is effectively improved, the productivity of the device is improved, the yield of the product formaldehyde is improved, and the economic and social benefits of enterprises are increased;
the method of the invention uses the home-made iron-molybdenum catalyst, can also achieve excellent catalytic effect, can break through foreign monopoly, solves the dilemma that the current iron-molybdenum catalyst is monopolized abroad, breaks the dilemma of long supply period and high price caused by that the iron and molybdenum completely depend on import, reduces the operation cost and technical risk of enterprises, and has obvious economic and social benefits.
The process uses a domestic iron-molybdenum catalyst and N2Waste gas of O or containing N2The mixture of the waste gas of O and air is used as an oxidant, and the requirement of the existing process for preparing formaldehyde by oxidizing methanol by an iron-molybdenum method can be met.
Drawings
FIG. 1 is a process flow diagram of the present invention. 1. A booster fan; 2. a methanol pump; 3. a methanol evaporator; 4. a main reactor; 5. a hot water pump; 6. a condenser; 7. a first heat exchanger; 8. a second heat exchanger; 9. an absorption tower; 10. a formaldehyde pump; 11. a heat exchanger; 12. a process water pump; 13. a heat exchanger; 14. an ECS system.
Detailed Description
The following examples 1-6 are examples of the present invention and are intended to be illustrative of the invention only and not limiting.
Example 1
1. Filling a domestic EQ-101 type formaldehyde catalyst in the main reactor according to a normal program, and heating and driving according to the normal program;
2. adjusting the temperature of the heat conducting oil to be 265 ℃;
3. with a nitrogen content of N2The mixed gas of the adipic acid tail gas of O and air is used as an oxidant source, and O in the feed gas at the inlet is adjusted2The content is 4%, (2N)2O) content is 12%;
4. adjusting the content of methanol in the inlet feed gas to be 13.5%;
5. gradually increasing air quantity and adjusting airspeed to 10000h-1；
6. Sampling and analyzing the product quality after keeping for 1 week, and calculating the methanol conversion rate and the formaldehyde yield;
the results obtained in this example are shown in Table 1.
Example 2
1. Filling a domestic EQ-101 type formaldehyde catalyst in the main reactor according to a normal procedure, and starting according to the normal procedure;
2. adjusting the temperature of the heat conducting oil to be 265 ℃;
3. with a nitrogen content of N2The mixed gas of the adipic acid tail gas of O and air is used as an oxidant source, and O in the feed gas at the inlet is adjusted2The content is 3%, (2N)2O) content is 8%;
4. adjusting the content of methanol in the inlet feed gas to be 10.0%;
5. gradually increasing air quantity and adjusting airspeed to 10000h-1；
6. Sampling and analyzing the product quality after keeping for 1 week, and calculating the methanol conversion rate and the formaldehyde yield;
the results obtained in this example are shown in Table 1.
Example 3
1. Filling a domestic EQ-101 type formaldehyde catalyst in the main reactor according to a normal procedure, and starting according to the normal procedure;
2. adjusting the temperature of the heat conducting oil to be 265 ℃;
3. with a nitrogen content of N2The mixed gas of the adipic acid tail gas of O and air is used as an oxidant source, and O in the feed gas at the inlet is adjusted2The content is 5%, (2N)2O) content 15%;
4. adjusting the content of methanol in the inlet feed gas to be 18.0%;
5. gradually increasing air quantity and adjusting airspeed to 10000h-1；
6. Sampling and analyzing the product quality after keeping for 1 week, and calculating the methanol conversion rate and the formaldehyde yield;
the results obtained in this example are shown in Table 1.
Example 4
1. Filling a domestic EQ-101 type formaldehyde catalyst in the main reactor according to a normal procedure, and starting according to the normal procedure;
2. adjusting the temperature of the heat conducting oil to be 265 ℃;
3. with a nitrogen content of N2The mixed gas of the adipic acid tail gas of O and air is used as an oxidant source, and O in the feed gas at the inlet is adjusted2The content is 5%, (2N)2O) content 15%;
4. adjusting the content of methanol in the inlet feed gas to 16.0%;
5. gradually increasing air quantity and adjusting airspeed to 10000h-1；
6. Sampling and analyzing the product quality after keeping for 1 week, and calculating the methanol conversion rate and the formaldehyde yield;
the results obtained in this example are shown in Table 1.
Example 5
1. Filling a domestic EQ-101 type formaldehyde catalyst in the main reactor according to a normal procedure, and starting according to the normal procedure;
2. adjusting the temperature of the heat conducting oil to be 265 ℃;
3. with a nitrogen content of N2The mixed gas of the adipic acid tail gas of O and air is used as an oxidant source, and O in the feed gas at the inlet is adjusted2The content is 8%, (2N)2O) content is 8%;
4. adjusting the content of methanol in the inlet feed gas to be 14.5%;
5. gradually increasing air quantity and adjusting airspeed to 10000h-1；
6. Sampling and analyzing the product quality after keeping for 1 week, and calculating the methanol conversion rate and the formaldehyde yield;
the results obtained in this example are shown in Table 1.
Example 6
1. Filling a domestic EQ-101 type formaldehyde catalyst in the main reactor according to a normal procedure, and starting according to the normal procedure;
2. adjusting the temperature of the heat conducting oil to 240 ℃;
3. with a nitrogen content of N2The mixed gas of the adipic acid tail gas of O and air is used as an oxidant source, and O in the feed gas at the inlet is adjusted2The content is 8%, (2N)2O) content is 8%;
4. adjusting the content of methanol in the inlet feed gas to be 14.5%;
5. increasing the wind graduallyThe amount and the space velocity are adjusted to 10000h-1；
6. Sampling and analyzing the product quality after keeping for 1 week, and calculating the methanol conversion rate and the formaldehyde yield;
the results obtained in this example are shown in Table 1.
Example 7
1. Filling a domestic EQ-101 type formaldehyde catalyst in the main reactor according to a normal procedure, and starting according to the normal procedure;
2. adjusting the temperature of the heat conducting oil to 290 ℃;
3. with a nitrogen content of N2The mixed gas of the adipic acid tail gas of O and air is used as an oxidant source, and O in the feed gas at the inlet is adjusted2The content is 8%, (2N)2O) content is 8%;
4. adjusting the content of methanol in the inlet feed gas to be 14.5%;
5. gradually increasing air quantity and adjusting airspeed to 10000h-1；
6. Sampling and analyzing the product quality after keeping for 1 week, and calculating the methanol conversion rate and the formaldehyde yield;
the results obtained in this example are shown in Table 1.
Comparative example 1
1. Filling a formaldehyde catalyst imported from foreign countries into the main reactor according to a normal procedure, and starting according to the normal procedure;
2. adjusting the temperature of the heat conducting oil to be 265 ℃;
3. adjusting O in inlet feed gas2The content is 11%, (2N)2O) content is 0%;
4. adjusting the content of methanol in the inlet feed gas to be 10.0%;
5. gradually increasing air quantity and adjusting airspeed to 10000h-1；
6. Sampling and analyzing the product quality after keeping for 1 week, and calculating the methanol conversion rate and the formaldehyde yield;
the results obtained in this example are shown in Table 1.
Table 1 catalyst composition and property results for each example
The specific preparation process steps can be as follows:
1) fresh air, containing N2Mixing the waste gas of O and the circulating tail gas according to a certain proportion to obtain (O)2+2N2O) mixed gas with certain content enters a booster fan (1) for boosting;
2) air at the air outlet of the booster fan (1) is sent to a methanol evaporator (3) and is mixed with methanol sent by a methanol pump (2);
3) the methanol is vaporized in the evaporator (3) to form a raw material gas containing methanol with a certain concentration;
4) raw material gas enters a main reactor (4), on an iron-molybdenum catalyst, the catalyst is heated by heat conduction oil to perform oxidation reaction to generate formaldehyde reaction gas, the reaction temperature of the catalyst can be regulated and controlled by regulating and controlling the temperature of the heat conduction oil, the general adjustable range of the heat conduction oil is 240-290 ℃, and the controlled catalytic temperature range is 280-330 ℃. The temperature of the heat conducting oil in the embodiment can be specifically regulated and controlled to be 240 ℃, 265 ℃ and 290 ℃. The gas is cooled by a heat exchanger (7) and then enters an absorption tower (9), most of formaldehyde is absorbed by dilute formaldehyde solution from a pump (10) and process water from a process water pump (12) to obtain formaldehyde, wherein the dilute formaldehyde solution from the formaldehyde pump (10) is cooled by a heat exchanger (13) in advance before entering the absorption tower, hot water in the heat exchanger is pumped into an evaporator (3) by a hot water pump (5) to heat methanol for gasification, the cooled water returns to a first heat exchanger to be heated, and the first heat exchanger recovers reaction heat to heat water; the heat generated by the main reactor (4) is carried into the condenser (6) by the heat conducting oil; then generating high pressure steam in a second heat exchanger (8);
5) the residual gas is partially sent to be mixed with fresh air, and part of the residual gas enters an ECS (exhaust gas catalytic purification) system for catalytic combustion;
6) and the waste gas out of the ECS system (14) is discharged into the atmosphere after energy is recovered by a heat exchanger (11).

Claims (10)

1. A production process for preparing formaldehyde by oxidizing methanol with an iron-molybdenum method is characterized by comprising the following steps: using a catalyst containing N2Waste gas of O or containing N2Mixture of exhaust gas of O and air as oxygenOxidizing methanol with catalyst by iron-molybdenum method to prepare formaldehyde.
2. The production process for preparing formaldehyde by methanol oxidation with the iron-molybdenum method according to claim 1, which is characterized in that: said group containing N2The waste gas of O is tail gas generated in the production process of adipic acid, and N discharged in the caprolactam or nitric acid industry2And (4) O waste gas.
3. The production process for preparing formaldehyde by methanol oxidation with the iron-molybdenum method according to claim 1, which is characterized in that: said N is2Waste gas of O or containing N2In the mixed gas of the waste gas of O and air and the raw material gas of methanol, N2Conversion of O to O2Metering (O)2+N2O) content of 11-20%, wherein N2The content of O is 8 to 15 percent, and O2The content is 3% -8%.
4. The production process for preparing formaldehyde by methanol oxidation with the iron-molybdenum method according to claim 1, which is characterized in that: control of content of N2Waste gas of O or containing N2The flow ratio of the mixed gas of the waste gas of O and air to the raw material gas of methanol is 1: 1-1: 5.
5. The production process for preparing formaldehyde by methanol oxidation with the iron-molybdenum method according to claim 1, which is characterized in that: said N is2Waste gas of O or containing N2The content of methanol in the mixed gas of the waste gas of O and air and the raw material gas of methanol is 10 to 18 percent.
6. The production process for preparing formaldehyde by methanol oxidation with the iron-molybdenum method according to claim 1, which is characterized in that: the temperature range of the iron-molybdenum method catalysis is 280-330 ℃.
7. The production process for preparing formaldehyde by methanol oxidation with the iron-molybdenum method according to claim 1, which is characterized in that: the iron-molybdenum catalyst for preparing formaldehyde by oxidizing methanol by using an iron-molybdenum method is an EQ-101 type domestic formaldehyde catalyst of Hua Xuan science and technology Co.
8. The production process for preparing formaldehyde by methanol oxidation with the iron-molybdenum method according to claim 1, which is characterized in that: the tail gas generated in the process is used as circulating tail gas and contains N2Waste gas of O or containing N2Mixing the waste gas of O with the mixed gas of air to prepare raw material gas, and oxidizing methanol by an iron-molybdenum method to prepare formaldehyde.
9. The production process for preparing formaldehyde by methanol oxidation with the iron-molybdenum method according to claim 1, which is characterized in that:
1) providing a compound containing N2Waste gas of O or containing N2The mixed gas of the waste gas of the O and the air enters a booster fan to be boosted;
2) boosting the pressure of the booster fan and mixing the boosted pressure with the methanol;
3) the raw material gas containing methanol with certain concentration is formed after heat absorption and vaporization in the evaporator;
4) and the raw material gas enters a main reactor and is subjected to oxidation reaction under the catalysis of an iron-molybdenum catalyst to generate formaldehyde reaction gas, and the formaldehyde reaction gas enters an absorption tower after being cooled and is absorbed by the absorption tower to obtain the product formaldehyde.
10. The production process for preparing formaldehyde by methanol oxidation with the iron-molybdenum method according to claim 9, which is characterized in that:
fresh air, containing N2Preparing the waste gas of O to obtain (O)2+2N2O) mixed gas with certain content;
the residual gas which is not absorbed by the absorption tower is mixed with fresh air according to the requirement and contains N2Preparing the waste gas of O to obtain (O)2+2N2O) mixed gas with certain content.
CN201910865069.3A 2019-09-12 2019-09-12 Production process for preparing formaldehyde by oxidizing methanol with iron-molybdenum method Pending CN110790646A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115181027A (en) * 2022-07-25 2022-10-14 万华化学集团股份有限公司 Method for controlling refractory aniline impurities in waste brine in DAM production process

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
TSONG-JEN YANG等: "Partial oxidation of methanol to formaldehyde over molybdenum oxide on silica", 《JOURNAL OF CATALYSIS》 *
张雄斌等: "EQ-101型铁钼甲醛合成催化剂的工业应用", 《煤化工》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115181027A (en) * 2022-07-25 2022-10-14 万华化学集团股份有限公司 Method for controlling refractory aniline impurities in waste brine in DAM production process
CN115181027B (en) * 2022-07-25 2023-09-22 万华化学集团股份有限公司 Method for controlling refractory aniline impurities in waste brine in DAM production process
WO2024021969A1 (en) * 2022-07-25 2024-02-01 万华化学集团股份有限公司 Method for controlling aniline impurities that are difficult to treat in waste brine in dam production process

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