CN106268247A - A kind of catalytic absorption method of formaldehyde - Google Patents
A kind of catalytic absorption method of formaldehyde Download PDFInfo
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- CN106268247A CN106268247A CN201510267411.1A CN201510267411A CN106268247A CN 106268247 A CN106268247 A CN 106268247A CN 201510267411 A CN201510267411 A CN 201510267411A CN 106268247 A CN106268247 A CN 106268247A
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Abstract
This application discloses a kind of catalytic absorption method of formaldehyde, by formaldehyde absorption to liquid-absorbant from the gaseous phase materials containing formaldehyde, it is characterised in that described liquid-absorbant contacts with solid catalyst；Described solid catalyst does not dissolves in described liquid-absorbant.Disclosed herein as well is said method application in Formaldehyde Production.Disclosed herein as well is the prepn. of formaldehyde using said method.Use the present processes, absorption process can be carried out with lower temperature, be more beneficial for obtaining the formalin of high concentration, required absorption tower number of theoretical plate can also be reduced simultaneously.
Description
Technical field
The application relates to a kind of catalytic absorption method of formaldehyde, belongs to chemical field.
Background technology
The production of current industrial formaldehyde mainly with methanol as raw material, use methanol air oxidation legal system
?.Methanol air oxidizing process is divided into methanol excessive oxidation method i.e. silver catalytic oxidation, air excess oxidation
Method i.e. ferrum molybdenum catalytic oxidation, and methanol excessive oxidation method is divided into traditional handicraft and circulation of tail gas work
Skill.In addition with methylal oxidation method.In any of the above prepn. of formaldehyde, material benzenemethanol or first
After acetal oxidation by air in the reactor, it is quenched to uniform temperature entrance absorption tower water and inhales
Receive.Sometimes it is also adopted by producing the aqueous solution of urea of downstream product needs or alcohols feedstock as absorbent.
When formaldehyde is only absorbed by the water, first formaldehyde is dissolved in water with monomer molecule form, then formaldehyde with
Water generation condensation reaction generates the polyoxymethylene glycol of a series of different polymerization degrees, and then consumes solution
Middle formaldehyde monomers molecule, to maintain the motive force of formaldehyde absorption process.And formaldehyde and the condensation reaction of water
Speed is slow, is difficult to quickly reach balance, it is difficult to obtain the formalin of very high concentration.Formaldehyde
Situation about being absorbed by alcohols is similar to, still slower with the reaction of alcohols due to formaldehyde, it is difficult to obtain the highest
The formaldehyde alcoholic solution of concentration.
Summary of the invention
An aspect according to the application, it is provided that a kind of catalytic absorption method of formaldehyde, the method can
So that the formalin of high concentration can be obtained, and use relatively low absorption temperature, institute can be reduced simultaneously
The absorption tower number of theoretical plate needed, and then reduce energy consumption.
The catalytic absorption method of described formaldehyde, by formaldehyde absorption to liquid from the gaseous phase materials containing formaldehyde
In body absorbent, it is characterised in that described liquid-absorbant contacts with solid catalyst；Described solid
Catalyst does not dissolves in described liquid-absorbant.
In the application, " described solid catalyst does not dissolves in described liquid-absorbant ", refer to described solid
Catalyst dissolubility in described liquid-absorbant is respectively less than 1g/100g solvent.
The process absorbing formaldehyde by the aqueous absorbent of liquid phase is a kind of MODEL OF CHEMICAL ABSORPTION PROCESS.Formaldehyde and water
Methylene glycol (HOCH can be generated by Formulas I generation condensation reaction2OH), methylene glycol can be continued by Formula II
Condensation generates the polyoxymethylene glycol of a series of different polymerization degrees, and its molecular formula is HO (CH2O)nH
(being abbreviated as MGn), above reaction is reversible reaction.
When using containing alcohol absorbent to absorb formaldehyde, similar to using aqueous situation, formaldehyde is with alcohol also
Condensation reaction can be occurred to generate the hemiformal of a series of different polymerization degrees, as formaldehyde is permissible with methanol
Generating molecular formula according to trans III and formula IV is HO (CH2O)nCH3A series of hemiformal chemical combination
Thing.Therefore alcohols can also be used under some particular cases as absorbent.
Generally, in formalin, HO (CH2O)nN in H is the biggest, formaldehyde monomers molecule
Content the lowest, and then liquid phase to absorb the motive force of formaldehyde from gas phase the biggest.Because liquid phase Chinese style
The response speed of I～IV is relatively slow, and therefore the conditioning step of formaldehyde absorption process is the reaction of Formulas I～IV
Process.The technical scheme of the application, the liquid-absorbant absorbing formaldehyde contacts with solid catalyst, logical
Cross employing solid catalyst, by a relatively large margin improve Formulas I～the response speed of IV in liquid phase so that
In liquid phase, formaldehyde monomers molecule maintains low concentration all the time, and then liquid-absorbant can be kept from gas
Absorb formaldehyde process in mutually and possess bigger motive force all the time.Therefore the formaldehyde of technical scheme
Catalytic absorption process efficiency is high, can at a lower temperature, absorb more formaldehyde with relatively low energy consumption,
Obtain the formalin of higher concentration.
Preferably, described solid catalyst contains Si oxide, activated carbon, metal-oxide, inorganic
At least one in salt.
Described solid catalyst can effectively be catalyzed the reaction of liquid phase Chinese style I～IV, does not generate it simultaneously
He affects the by-product of formaldehyde quality.
Use the aqueous and/or liquid-absorbant of alcohol, from the gaseous phase materials containing formaldehyde, absorb formaldehyde
Time, after formaldehyde is dissolved in absorbent, described liquid-absorbant contacts with described solid catalyst,
Rapid and water or alcohol generation condensation reaction under described solid catalyst effect, and quickly reach or close
Chemical equilibrium.Compared with the situation that there is not catalyst, due to formaldehyde monomers molecule rapidly and as far as possible
Many conversions consume, and therefore in solution, the concentration of formaldehyde monomers molecule is lower, formaldehyde absorption process
Motive force bigger, then use less absorbent consumption to be fully absorbed by formaldehyde, thus obtain
The formalin of higher concentration.Simultaneously as the motive force absorbed is bigger, absorption efficiency improves, and reaches
Absorption tower number of theoretical plate required for same absorption target is the least, reduce further energy consumption.
It is further preferred that described solid catalyst is selected from silicon dioxide, aluminium oxide, activated carbon, silicon
At least one in acid magnesium, potassium aluminosilicate, sodium aluminosilicate.
Preferably, containing water and/or alcohol compound in described liquid-absorbant.When described liquid absorbs
When agent is aqueous, water can be comprised only, it is also possible to containing water and carbamide.The preferred first of described alcohol compound
Alcohol or ethanol.
Being preferably carried out mode as one, described liquid-absorbant is selected from water, aqueous solution of urea, first
At least one in alcohol, ethanol.
Preferably, the absorption process of formaldehyde is carried out at a temperature of less than 80 DEG C.Formula II and formula IV
Condensation reaction be exothermic reaction, the most relatively low absorption temperature be conducive to the balance of this serial reaction to
The direction generating polyoxymethylene glycol or hemiformal is moved, and the most relatively low absorption temperature is the most favourable
In improving the saturated concentration that formaldehyde dissolves in water, beneficially formaldehyde absorption.
Under conditions of described solid catalyst exists, even if it is relatively low to absorb temperature, formaldehyde and water or alcohol
A series of condensation reactions also can reach response speed faster, the bottle of formaldehyde absorption process will not be become
Neck.Therefore, compared with the prior art not having catalyst, the technical scheme of the application can be adopted
By lower absorption temperature, improve suction efficiency, it is also possible to the absorption tower number of theoretical plate required for reduction,
It is more favorable to obtain the formalin of high concentration simultaneously.
It is further preferred that the temperature range upper limit of the absorption process of formaldehyde selected from 50 DEG C, 60 DEG C,
80 DEG C, lower limit is selected from 20 DEG C, 25 DEG C, 30 DEG C, 31 DEG C, 40 DEG C.It is further preferred that formaldehyde
Absorption process carry out at a temperature of 20 DEG C～60 DEG C.In this temperature range, exist keeping formaldehyde
In liquid absorbent while high-dissolvability, it is more beneficial for providing Formulas I～the response speed of IV.
The absorption process of formaldehyde can complete in one section of absorption plant, it is also possible to a point multistage is carried out.Institute
State the multistage that multistage can be an absorption tower, it is also possible to be multiple absorption towers.
Preferably, absorption process divides two sections to carry out.Described two sections because of each section of flow and temperature isoparametric
Difference, can use different flows and temperature, diameter and the height can be the same, it is also possible to different.
Preferably, the diameter of the first absorber portion is more than the second absorber portion.
Preferably, the absorption process of the first absorber portion is carried out at a temperature of 30 DEG C～80 DEG C.
Preferably, the absorption process of the second absorber portion is carried out at a temperature of 20 DEG C～45 DEG C.
The described gaseous phase materials containing formaldehyde first passes through the first absorber portion again by the second absorber portion.
Another aspect according to the application, it is provided that the catalytic absorption method of any of the above-described kind of formaldehyde exists
Application in Formaldehyde Production.
Another aspect according to the application, it is provided that a kind of method preparing high-concentration formaldehyde product,
Prepare formaldehyde with methanol for raw material, obtain the gaseous phase materials containing formaldehyde, it is characterised in that in employing
The catalytic absorption method stating any one formaldehyde absorbs formaldehyde from the gaseous phase materials containing formaldehyde, obtains height
The formaldehyde products of concentration.
Preparing formaldehyde with methanol for raw material, its reaction aoxidizes for methanol, uses air or oxygen as oxygen
Agent, uses silver catalyst or iron-molybdenum catalyst, the most also uses steam and/or nitrogen as dilute
Outgassing.
The beneficial effect that the application can produce includes:
1) formaldehyde catalytic absorption method provided herein is used, from the gaseous phase materials containing formaldehyde
Middle absorption formaldehyde, it is possible to obtain the formalin of higher concentration.
2) method provided herein, it is possible to reach excellent absorption at a temperature of relatively low absorption
Effect.
3) method provided herein, has higher absorption efficiency, it is possible to required for reduction
Absorption tower number of theoretical plate, and then reduce energy consumption.
4) method provided herein, the method preparing high-concentration formaldehyde product, it is possible to relatively low
Cost and energy consumption obtain the formaldehyde products of higher concentration.
Detailed description of the invention
Below in conjunction with embodiment in detail the application is described in detail, but the application is not limited to these embodiments.
If no special instructions, the raw material in embodiments herein and catalyst are all purchased by commercial sources
Buy.
Embodiments herein is analyzed method as follows:
Use the 7890A gas chromatograph (thermal conductivity cell detector) that Agilent company produces, to each thing
In material, the content of formaldehyde is analyzed.
Embodiment 1
The preparation of formaldehyde
Methanol, water heating vaporization after with preheating after air be mixed into the reactor equipped with silver catalyst
Carry out oxidative dehydrogenation generate formaldehyde, methanol inlet amount 244ml/h, water inlet amount 100ml/h,
Air feed amount 200l/h, reaction temperature 620 DEG C, obtain reaction gas after reaction.
The absorption of formaldehyde
Reaction gas is vented after being cooled fast to 130 DEG C after 1 glass absorbing column absorbs formaldehyde.Absorb
Column internal diameter 30mm, equal mixed packing φ 3 × 3mm rustless steel Dixon ring filler and φ 2 × 3-5mm bar
Shape aluminium oxide catalyst, Dixon ring filler is 4: 1 with the volume ratio of catalyst, and filling height is 2m.
Reaction gas enters from the bottom of absorbing column, top is discharged.Absorbing column head temperature 30 DEG C, bottom temp
60℃.Fresh absorption water (flow 35.3ml/h) enters from the top of absorbing column, at bottom collection
Absorbing liquid cooling rear portion returns circulation from the middle part of absorbing column, and circulating load is 4200ml/h, its
Remaining as formalin product extraction, produced quantity is 340ml/h, and content of formaldehyde is 45wt%, with putting
The formaldehyde that air is discharged accounts for the 0.1wt% generating formaldehyde total amount.
Embodiment 2～6
The preparation of formaldehyde
The preparation process of formaldehyde is same as in Example 1, wherein methanol inlet amount, air feed amount, water
Or nitrogen feed amount, reaction temperature are shown in Table 1.
The absorption of formaldehyde
Reaction gas is put after being cooled fast to 130 DEG C after the glass absorbing column of two series connection absorbs formaldehyde
Empty.First absorbing column internal diameter 30mm, the second absorbing column internal diameter 20mm, equal mixed packing φ 3 × 3mm
Rustless steel Dixon ring filler and φ 2 × 3-5mm bar shaped aluminium oxide catalyst, Dixon ring filler and catalysis
The volume ratio of agent is 4: 1, and filling is highly 1m.Reaction gas enters from the bottom of the first absorbing column,
Top is discharged, and subsequently into the bottom of the second absorbing column, then discharges from the top of the second absorbing column.Inhale
Receive agent to enter from the top of the second absorbing column, after the absorbent cooling of the bottom collection of the second absorbing column
A part returns circulation from the middle part of absorbing column, and circulating load is shown in Table 1, and remainder enters first
The top of absorbing column.The absorbing liquid cooling rear portion top from absorbing column of the first absorbing column bottom collection
Portion returns circulation, and circulating load is shown in Table 1, and remaining is as formalin product extraction, produced quantity and
Content of formaldehyde is shown in Table 1.First, second absorbing column head temperature, bottom temp, drop a hint
Formaldehyde accounts for generation formaldehyde total amount and is shown in Table 1.
Table 1
Notea: wherein the inlet amount of first alcohol and water is mark condition fluid flow；Air, nitrogen are mark condition gas flow.
Noteb: weight/mass percentage composition is the aqueous solution of urea of 30%.
Notec: concentration of formaldehyde represents with weight/mass percentage composition.
Noted: emptying formaldehyde accounting is " formaldehyde total amount * 100% that the formaldehyde/reaction discharged with dropping a hint generates ".
Comparative example 1
The preparation of formaldehyde
Consistent with embodiment 2.
The absorption of formaldehyde
Consistent with embodiment 2, simply it is provided without catalyst.In the formalin of extraction, formaldehyde quality is dense
Degree is 42wt%, accounts for the 12wt% generating formaldehyde total amount with the formaldehyde discharged of dropping a hint.
Comparative example 1 the most relatively, illustrates to absorb identical containing under identical acceptance condition
Formaldehyde gaseous phase materials, when there is no a catalyst formaldehyde can not be fully absorbed, obtained formalin
Concentration of formaldehyde relatively low.Embodiment 2 have employed solid catalyst, and the formaldehyde in reaction gas is the completeest
Hypersorption, obtained formalin concentration of formaldehyde the highest.
The above, be only several embodiments of the application, and the application not does any type of limit
System, although the application with preferred embodiment disclose as above, but and be not used to limit the application, any
Those skilled in the art, in the range of without departing from technical scheme, utilize above-mentioned taking off
The technology contents shown makes a little variation or modification is all equal to equivalence case study on implementation, belongs to technology
In aspects.
Claims (10)
1. a catalytic absorption method for formaldehyde, by formaldehyde absorption from the gaseous phase materials containing formaldehyde
In liquid-absorbant, it is characterised in that described liquid-absorbant contacts with solid catalyst；Described
Solid catalyst does not dissolves in described liquid-absorbant.
Method the most according to claim 1, it is characterised in that described solid catalyst contains
At least one in Si oxide, activated carbon, metal-oxide, inorganic salt.
Method the most according to claim 1, it is characterised in that described solid catalyst is selected from
At least one in silicon dioxide, aluminium oxide, activated carbon, magnesium silicate, potassium aluminosilicate, sodium aluminosilicate.
Method the most according to claim 1, it is characterised in that contain in described liquid-absorbant
There are water and/or alcohol compound.
Method the most according to claim 1, it is characterised in that described liquid-absorbant is selected from
At least one in water, aqueous solution of urea, methanol, ethanol.
Method the most according to claim 1, it is characterised in that the absorption process of formaldehyde is not
Carry out at a temperature of more than 80 DEG C.
Method the most according to claim 1, it is characterised in that the absorption process of formaldehyde is at 20 DEG C
～carry out at a temperature of 60 DEG C.
Method the most according to claim 1, it is characterised in that absorption process divides two sections to carry out；
The absorption process of the first absorber portion is carried out at a temperature of 30 DEG C～80 DEG C；
The absorption process of the second absorber portion is carried out at a temperature of 20 DEG C～45 DEG C；
The described gaseous phase materials containing formaldehyde first passes through the first absorber portion again by the second absorber portion.
9. method application in Formaldehyde Production described in any one of claim 1 to 8.
10. the method preparing high-concentration formaldehyde product, prepares formaldehyde with methanol for raw material, obtains
Gaseous phase materials containing formaldehyde, it is characterised in that use according to described in any one of claim 1 to 8
Method absorbs formaldehyde from the gaseous phase materials containing formaldehyde, obtains the formaldehyde products of high concentration.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510267411.1A CN106268247A (en) | 2015-05-22 | 2015-05-22 | A kind of catalytic absorption method of formaldehyde |
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| CN201510267411.1A CN106268247A (en) | 2015-05-22 | 2015-05-22 | A kind of catalytic absorption method of formaldehyde |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112705274A (en) * | 2019-10-24 | 2021-04-27 | 中国石油化工股份有限公司 | Catalyst regeneration and formaldehyde recovery method |
| CN115494164A (en) * | 2021-06-18 | 2022-12-20 | 中国科学院大连化学物理研究所 | Method for detecting formaldehyde in gas-solid heterogeneous catalytic reaction process |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1036755A (en) * | 1988-02-03 | 1989-11-01 | 旭化成工业株式会社 | The method for preparing formaldehyde and derivative thereof |
| CN1074211A (en) * | 1992-01-10 | 1993-07-14 | 北京维尼纶厂 | A kind of method of producing concentrated formaldehyde and industrial formol simultaneously |
| CN101898943A (en) * | 2010-06-04 | 2010-12-01 | 洪正鹏 | Method for synthesizing polyoxymethylene dimethyl ethers |
| CN103339094A (en) * | 2011-01-26 | 2013-10-02 | 宝理塑料株式会社 | Method for producing hemiformal concentrate and method for producing formaldehyde gas |
| CN203469770U (en) * | 2013-08-05 | 2014-03-12 | 桂林汇众化工设备有限公司 | Two-stage circulation system of 1# absorption tower |
| CN104610031A (en) * | 2014-12-31 | 2015-05-13 | 湖北沙隆达股份有限公司 | Production method of high-concentration formaldehyde |
-
2015
- 2015-05-22 CN CN201510267411.1A patent/CN106268247A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1036755A (en) * | 1988-02-03 | 1989-11-01 | 旭化成工业株式会社 | The method for preparing formaldehyde and derivative thereof |
| CN1074211A (en) * | 1992-01-10 | 1993-07-14 | 北京维尼纶厂 | A kind of method of producing concentrated formaldehyde and industrial formol simultaneously |
| CN101898943A (en) * | 2010-06-04 | 2010-12-01 | 洪正鹏 | Method for synthesizing polyoxymethylene dimethyl ethers |
| CN103339094A (en) * | 2011-01-26 | 2013-10-02 | 宝理塑料株式会社 | Method for producing hemiformal concentrate and method for producing formaldehyde gas |
| CN203469770U (en) * | 2013-08-05 | 2014-03-12 | 桂林汇众化工设备有限公司 | Two-stage circulation system of 1# absorption tower |
| CN104610031A (en) * | 2014-12-31 | 2015-05-13 | 湖北沙隆达股份有限公司 | Production method of high-concentration formaldehyde |
Non-Patent Citations (1)
| Title |
|---|
| 何幸等: "甲缩醛催化氧化制浓甲醛催化剂及工艺研究", 《精细化工原料及中间体》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112705274A (en) * | 2019-10-24 | 2021-04-27 | 中国石油化工股份有限公司 | Catalyst regeneration and formaldehyde recovery method |
| CN115494164A (en) * | 2021-06-18 | 2022-12-20 | 中国科学院大连化学物理研究所 | Method for detecting formaldehyde in gas-solid heterogeneous catalytic reaction process |
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Application publication date: 20170104 |