Formaldehyde absorption treating fluid and formaldehyde absorber thereof

Abstract

The invention provides a formaldehyde absorption treating fluid and a formaldehyde absorber thereof, and belongs to the technical field of formaldehyde treatment. The formaldehyde absorption treating fluid comprises the following raw materials in parts by weight: 70-150 parts of a primary amino-containing compound, 0.1-1 part of a catalyst and 10-30 parts of a 3A molecular sieve. The formaldehyde absorption instrument is prepared from the formaldehyde absorption treatment liquid. According to the formaldehyde absorption treating fluid disclosed by the invention, formaldehyde and primary amine in the absorption treating fluid can be subjected to chemical reaction to generate aldimine, and meanwhile, one molecule of water is eliminated, so that the purpose and the effect of thoroughly eliminating formaldehyde are achieved, and the 3A molecular sieve is used for absorbing water molecules generated in the reaction to realize absorption, conversion and elimination of formaldehyde.

Description

Technical Field

[0001] The invention relates to the technical field of formaldehyde treatment, and in particular to a formaldehyde absorption treatment liquid and a formaldehyde absorption device thereof. Background Art

[0002] Formaldehyde is the simplest aldehyde molecule with active chemical properties and strong toxicity. It is widely present in nature and human living environment. It, acetaldehyde, acrolein, etc. are one of the aldehydes with special toxic effects. Formaldehyde is especially toxic. It severely irritates the skin, eyes and mucous membranes, causing rhinitis, conjunctivitis, skin allergies, bronchitis and other diseases. If you are in an environment containing this substance for a long time, it will cause serious diseases, such as drowsiness, gastroenteritis or nail pain, and in severe cases it will cause leukemia.

[0003] Ozone ions have strong oxidizing properties and are usually used as disinfectants for tableware and other purposes. They can also react with formaldehyde to eliminate formaldehyde. However, ozone (O3) itself is also one of the indoor pollutants. The 8-hour average concentration limit of ozone (O3) is clearly listed in my country's "Ambient Air Quality Standard" (GB3095-2012): the first-level standard is 100ug / m 3 , the secondary standard is 160ug / m 3 Usually, places where ozone disinfection is used are closed. After the disinfection is completed, it takes half an hour for the ozone ions in the environment to be inactivated before they can come into contact with the human body. Using ozone to eliminate formaldehyde is equivalent to fighting poison with poison. When ozone is excessive, it will also cause harm to the human body.

[0004] There are also a large number of formaldehyde scavengers in the prior art. For example, patent CN105727495A discloses that a micro-crosslinked polymer containing an amine group is obtained by polymerization reaction and Hofmann degradation reaction at 60-90°C, and the micro-crosslinked polymer is mixed with glacial acetic acid, water, etc. to obtain a formaldehyde spray liquid for the surface of a carpet; patent CN104645800A discloses that divinyltriamine and methyl acrylate are subjected to a condensation reaction at a certain temperature to synthesize a hyperbranched polymer containing an amine group, and then mixed with an auxiliary agent to obtain a polymer formaldehyde scavenger; patent CN1038 94042A discloses the use of urea, combined with the cyclic structure of cyclodextrin, and uniformly mixed in water to prepare a formaldehyde scavenger aqueous solution; Patent CN101658759A discloses the use of semicarbazide, ethylene urea and polyacrylamide diluent to synthesize an alkaline formaldehyde absorbent at 50-60°C; Patent CN109316939A discloses adding a primary amine compound to deionized water, stirring to dissolve it, obtaining a solution, and then using an acidic substance to adjust the pH value of the solution to 2-6, and then adding an auxiliary agent and stirring evenly to obtain a formaldehyde absorbent.

[0005] The essence of all the above patents is to first subject amine compounds to various reactions to synthesize urea or amide compounds or polymers, and then dissolve them in acidic or alkaline aqueous solutions. Since formaldehyde itself can be dissolved in water, the introduction of such substances only makes formaldehyde more stable in water and increases the absorption amount. Formaldehyde and it will hardly react chemically in aqueous solution. The formaldehyde absorption liquid in the prior art can only be used to absorb formaldehyde, and cannot achieve the effect of completely eliminating formaldehyde through chemical reaction with formaldehyde. Therefore, it is of great significance to study a formaldehyde absorption treatment liquid and use it in a formaldehyde absorber to achieve complete removal of formaldehyde. Summary of the invention

[0006] The purpose of the present invention is to provide a formaldehyde absorption treatment liquid and a formaldehyde absorption device thereof, so as to solve the problem that formaldehyde cannot be completely eliminated in the prior art.

[0007] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0008] The present invention provides a formaldehyde absorption treatment liquid, which comprises the following raw materials in parts by weight: 70 to 150 parts of a compound containing a primary amino group, 0.1 to 1 part of a catalyst, and 10 to 30 parts of a 3A molecular sieve.

[0009] Preferably, the primary amino group-containing compound comprises one or more of epoxy resin modified organic amines, vinylamine adducts, vinylamine prepolymers, polyetheramines, amino-terminated polyethers, amino-terminated polyesters, fatty amines, alicyclic amines, aromatic amines, amide amines and amino acids containing primary amines.

[0010] Preferably, the organic amine in the epoxy resin-modified organic amine comprises pentamethylenediamine, methylpentamethylenediamine or meta-xylylenediamine.

[0011] Preferably, the aromatic amine comprises 4,4'-diaminodiphenylmethane; and the alicyclic amine comprises isophorone organic amine or 4,4'-diaminodicyclohexylmethane.

[0012] Preferably, the amino acids include one or more of glutamic acid, aspartic acid, lysine, arginine, histidine and glycine.

[0013] Preferably, the catalyst comprises one or more of organic zinc, organic bismuth and organic tin.

[0014] The present invention also provides a formaldehyde absorption apparatus, comprising the formaldehyde absorption treatment liquid described above.

[0015] Beneficial effects of the present invention:

[0016] The present invention obtains a formaldehyde absorption treatment liquid through chemical reaction synthesis and physical preparation, which is used for absorbing and anchoring formaldehyde. Polluted air containing formaldehyde is introduced into the absorption treatment liquid. Under the condition of heating to 60°C and the presence of a catalyst, trace formaldehyde contained in the air reacts chemically with the primary amine group in the absorption treatment liquid to generate aldimine, and a molecule of water is eliminated at the same time, thereby achieving the purpose and effect of completely removing formaldehyde. This is different from the formaldehyde collector in the prior art that only physically absorbs.

[0017] In the present invention, formaldehyde reacts chemically with the primary amine groups in the absorption treatment liquid to generate water, and the reaction is reversible. Since formaldehyde is a small molecule structure, the conversion rate of formaldehyde is less than 40% only by heating and adding a catalyst. In order to make the reaction more thorough, 3A molecular sieve (which cannot adsorb larger molecular formaldehyde) is added to absorb the water molecules generated in the reaction, thereby achieving absorption, conversion and elimination of formaldehyde.

[0018] The formaldehyde absorber of the present invention is a device that actively absorbs air, so that air is quickly drawn into the absorber, and the formaldehyde in the air is combined with the effective components through the absorption treatment liquid, and the purpose of eliminating formaldehyde is achieved through chemical reaction. The formaldehyde absorber of the present invention can operate continuously, continuously remove the formaldehyde that is slowly released in the environment, and keep the environment healthy and harmless. DETAILED DESCRIPTION

[0019] The present invention provides a formaldehyde absorption treatment liquid, which comprises the following raw materials in parts by weight: 70 to 150 parts of a compound containing a primary amino group, 0.1 to 1 part of a catalyst, and 10 to 30 parts of a 3A molecular sieve.

[0020] The aldehyde group in formaldehyde is a highly active functional group. It undergoes Michael addition reaction with the amino group, eliminating a molecule of water to generate an imino group. The reaction process is HCHO+H2N-R→CH3NH-R+H2O. Even the imino group can continue to react with formaldehyde.

[0021] In the present invention, the primary amino group-containing compound comprises one or more of epoxy resin modified organic amines, vinylamine adducts, vinylamine prepolymers, polyetheramines, amino-terminated polyethers, amino-terminated polyesters, fatty amines, alicyclic amines, aromatic amines, amide amines and amino acids containing primary amines.

[0022] In the present invention, the epoxy resin modified organic amine modifies the small molecule organic amine through the epoxy resin to generate a non-volatile macromolecular structure product, which not only reduces the toxicity and volatility of the organic amine, but also does not affect the continued reaction of the retained primary amino group with formaldehyde.

[0023] In the present invention, the organic amine in the epoxy resin-modified organic amine includes pentamethylenediamine, methylpentamethylenediamine, meta-xylylenediamine or diethylenetriamine.

[0024] In the present invention, the aromatic amine comprises 4,4'-diaminodiphenylmethane; the alicyclic amine comprises isophorone organic amine or 4,4'-diaminodicyclohexylmethane.

[0025] In the present invention, the amino acid comprises one or more of glutamic acid, aspartic acid, lysine, arginine, histidine and glycine.

[0026] In the present invention, the catalyst comprises one or more of organic zinc, organic bismuth and organic tin.

[0027] The present invention also provides a formaldehyde absorption apparatus, comprising the formaldehyde absorption treatment liquid described above.

[0028] The formaldehyde absorber of the present invention can raise the temperature to 50-70° C., thereby achieving the purpose of completely removing formaldehyde.

[0029] The technical solutions provided by the present invention are described in detail below in conjunction with the embodiments, but they should not be construed as limiting the protection scope of the present invention.

[0030] The reagents used in the examples of the present invention were purchased from the following manufacturers:

[0031] Diethylenetriamine: Japan Tosoh Co., Ltd.;

[0032] EP128 epoxy resin: Jiangsu Yangnong Chemical Co., Ltd.

[0033] Methylpentanediamine: INVISTA;

[0034] Oxalic acid: Weifang Chenyang Chemical Co., Ltd.

[0035] Toluene diisocyanate: Covestro, Germany;

[0036] Polyetheramine D230: Huntsman Corporation, USA;

[0037] Isophoronediamine and 4,4'-diaminodicyclohexylmethane: Yantai Wanhua Chemical Group;

[0038] Polyetheramine T403: Huntsman Corporation, USA;

[0039] Glutamic acid: Shandong Huatai Chemical Co., Ltd.;

[0040] 3A molecular sieve (granular packaging, pore size 0.3nm): Shanghai Jiuzhou Company;

[0041] Organic zinc catalyst A30: Dongguan Lisheng Chemical Co., Ltd.

[0042] Example 1

[0043] Place 200 g of diethylenetriamine in a 500 mL flask, heat to 65°C, then add EP128 epoxy resin in three times, a total of 190 g, stirring while adding, keep the temperature at 65°C for 3 hours, then heat to 100°C and keep warm for 30 minutes, and cool to obtain EP128 epoxy resin modified diethylenetriamine.

[0044] H2N-CH2-CH-NH-CH2-CH2-NH2+CH2(-O-)CH-R-CH-(-O-)CH2=H2N-CH2-CH-NH2-CH2-CH2-NH-CH2-CH2(-OH)-R-CH2(-OH)-CH2-HN-CH2-CH-NH2-CH2-CH2-NH2

[0045] The composition of the formaldehyde absorption treatment liquid is: 50 parts of EP128 epoxy resin modified diethylenetriamine, 30 parts of 4,4-diaminodicyclohexylmethane, 0.5 parts of organic zinc catalyst (A30), and 20 parts of 3A molecular sieve.

[0046] Example 2

[0047] 80 kg of methylpentanediamine was placed in a 150 L reactor, 20 kg of water was added, the reactor was heated to 60 ° C, and then 50 kg of oxalic acid was added in batches. After the oxalic acid was added, the temperature was raised to 90 ° C, and the reaction was kept warm for 2 hours. The temperature was continued to be raised to 105 ° C to gradually evaporate water and some unreacted methylpentanediamine, and the distilled fraction was condensed and collected. The temperature was continued to be raised to 160 ° C and kept warm for 1 hour. When no more water was evaporated, amide amine was obtained.

[0048]

[0049] The composition of the formaldehyde absorption treatment liquid is: 80 parts of amidoamine, 1 part of organic zinc catalyst (A30), and 30 parts of 3A molecular sieve.

[0050] Example 3

[0051] Place 67 kg of diethylenetriamine in a 150 L reactor, add 20 kg of water, heat the reactor to 60 ° C, and then add 50 kg of oxalic acid in batches. After adding the oxalic acid, raise the temperature to 90 ° C, keep the temperature for 2 hours, continue to raise the temperature to 105 ° C to gradually evaporate water and some unreacted methylpentanediamine, condense and collect the evaporated fraction, continue to raise the temperature to 160 ° C and keep it for 1 hour. When no more water is evaporated, amide polyamine is obtained.

[0052]

[0053] The composition of the formaldehyde absorption treatment liquid is: 80 parts of amide polyamine, 1 part of organic zinc catalyst (A30), and 30 parts of 3A molecular sieve.

[0054] Example 4

[0055] 170 kg of toluene diisocyanate was placed in a high-position reactor, and 40 kg of anhydrous ethanol was slowly dripped into the reactor. The temperature was controlled at 45 °C during the process. After the dripping was completed, the mixture was kept warm for 2 hours. Then the reacted materials were slowly dripped into a low-position reactor containing polyetheramine D230 (mass 240 kg). The temperature was controlled at 55 °C during the dripping process. After the dripping was completed, the mixture was kept warm for 2 hours. The temperature was then raised to 80 °C for reaction for 1 hour, and the mixture was cooled to obtain N-toluene ethyl formate-formamide modified amino-terminated polyether.

[0056] Reaction 1: CH3CH2OH+NCO-C6H6(-CH3)-OCN→CH3CH2OOC-NH-C6H6(-CH3)-OCN;

[0057] Reaction 2: NH2-{CH2-CH(-R)-O-} n -NH2+CH3CH2OOC-NH-(C6H6)(-CH3)-OCN→NH2-{CH2-CH(-R)-O-} n -NH-COO-C6H6(-CH3)-NH-COOCH2CH3;

[0058] The composition of the formaldehyde absorption treatment liquid is: 50 parts of N-toluene ethyl carbamate-formamide modified terminal amino polyether, 30 parts of PACM (4,4'-diaminodicyclohexylmethane), 1 part of organic zinc catalyst (A30), and 10 parts of 3A molecular sieve.

[0059] Example 5

[0060] The composition of the formaldehyde absorption treatment liquid is as follows: 40 parts of isophorone diamine, 20 parts of polyetheramine D400, 30 parts of PACM (4,4'-diaminodicyclohexylmethane), 1 part of organic zinc catalyst (A30), and 10 parts of 3A molecular sieve.

[0061] Example 6

[0062] The composition of the formaldehyde absorption treatment liquid is: 20 parts of glutamic acid, 10 parts of aspartic acid, 50 parts of polyetheramine T403, 30 parts of PACM (4,4'-diaminodicyclohexylmethane), 1 part of organic zinc catalyst (A30), and 10 parts of 3A molecular sieve.

[0063] The performance test of the formaldehyde absorption treatment liquid of Examples 1 to 6 was carried out as follows: 1000 ml of each of the formaldehyde absorption treatment liquids prepared in Examples 1 to 6 were placed in a 1 m 3In a closed space, 10 mg of formaldehyde was accurately weighed and placed in the closed space. The air containing formaldehyde was introduced into the absorption liquid through an air pump. After a 30-minute / 60-minute cycle, the formaldehyde content of the gas in the closed space was re-measured as shown in Table 1:

[0064] Table 1 Formaldehyde content test results

[0065]

[0066]

[0067] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A formaldehyde absorption treatment liquid, characterized in that: The formaldehyde absorption treatment liquid comprises the following raw materials in parts by weight: 70 to 150 parts of a compound containing a primary amino group, 0.1 to 1 part of a catalyst, and 10 to 30 parts of a 3A molecular sieve.

2. The formaldehyde absorption treatment liquid according to claim 1, characterized in that: The primary amino group-containing compound comprises one or more of epoxy resin modified organic amine, vinylamine adduct, vinylamine prepolymer, polyetheramine, amino-terminated polyether, amino-terminated polyester, fatty amine, alicyclic amine, aromatic amine, amide amine and amino acid containing primary amine group.

3. The formaldehyde absorption treatment liquid according to claim 2, characterized in that: The organic amine in the epoxy resin modified organic amine comprises pentamethylenediamine, methylpentamethylenediamine or meta-xylylenediamine.

4. The formaldehyde absorption treatment liquid according to claim 2, characterized in that: The aromatic amine comprises 4,4'-diaminodiphenylmethane; and the alicyclic amine comprises isophorone organic amine or 4,4'-diaminodicyclohexylmethane.

5. The formaldehyde absorption treatment liquid according to claim 2, characterized in that: The amino acids include one or more of glutamic acid, aspartic acid, lysine, arginine, histidine and glycine.

6. The formaldehyde absorption treatment liquid according to any one of claims 1 to 5, characterized in that: The catalyst comprises one or more of organic zinc, organic bismuth and organic tin.

7. A formaldehyde absorption instrument, characterized in that: A formaldehyde absorbent comprising the formaldehyde absorbent according to any one of claims 1 to 6.

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