CN105669601B - A kind of method of AKD product dehydrates - Google Patents

A kind of method of AKD product dehydrates Download PDF

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Publication number
CN105669601B
CN105669601B CN201610008103.1A CN201610008103A CN105669601B CN 105669601 B CN105669601 B CN 105669601B CN 201610008103 A CN201610008103 A CN 201610008103A CN 105669601 B CN105669601 B CN 105669601B
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China
Prior art keywords
akd
triethylamine
products
salt
pickling
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Expired - Fee Related
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CN201610008103.1A
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Chinese (zh)
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CN105669601A (en
Inventor
蒙鸿飞
梁立新
韩胜兵
李小利
沈精平
齐国栋
付振波
李晓明
王萍
边祥成
李莉
孟蕾
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Gansu Yinguang Juyin Chemical Industry Co Ltd
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Gansu Yinguang Juyin Chemical Industry Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D305/00—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms
    • C07D305/02—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings
    • C07D305/10—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings having one or more double bonds between ring members or between ring members and non-ring members
    • C07D305/12—Beta-lactones

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)

Abstract

The invention belongs to AKD preparation method fields, more particularly to a kind of method of AKD product dehydrates, after white picking being carried out by the mixture of the AKD to completing condensation reaction, triethylamine and triethylamine hydrochloride, hot blast film drying is carried out again, and triethylamine is recycled, obtained AKD products are fully dehydrated, depickling, and its moisture is less than 200ppm, acid number is less than 5ppm, reaches AKD product index requirements.Relative to traditional flash method AKD dewatering process, the present invention for low-temperature operation, without coking, the purity of products obtained therefrom is high, colourity is good.The present invention realizes aqueous AKD serialization dewatering process, and production capacity is high, and energy consumption is low, greatly reduces production cost.Compared with traditional flash method AKD dewatering process, the technological operation, the part HCI in AKD can be steamed with hydrochloric acid, the acid number of products obtained therefrom is significant lower, it is easy to up to standard.

Description

A kind of method of AKD product dehydrates
Technical field
The invention belongs to AKD manufacturing fields, and in particular to a kind of method of AKD product dehydrates.
Background technology
Alkyl ketene dimer (Alkyl Ketene Dimer, abbreviation AKD) is a kind of paper making pulp neutral sizing agent, main It is used for high-level thinking ability, food wrapper, art paper, offset printing paper, carbon paper, autochromy body paper, archival paper, ticket Demonstrate,prove the production of the high-grade paper products such as paper.
Traditional handicraft AKD dehydration is thick by the oil phase for completing white picking using autoclave constant-pressure and high-temperature flash process AKD (water content 0.8~1%) is added directly into the stirred tank of jacketed, and by jacket for heat exchange, temperature of charge is heated to 120 DEG C, at ambient pressure using the method for flash distillation, complete the dehydration of AKD products.The defects of following three aspects be present in the technique：
(1) intermittently operated, complex procedures, arid cycle are grown, and drying capacity is poor；
(2) operation temperature is high, it is easy to causes the coking at high temperature of AKD products, directly influences product purity and colourity；
(3) the drying process products obtained therefrom, moisture and acid number are higher.
The content of the invention
It is an object of the invention to provide a kind of method of AKD product dehydrates, will complete AKD, the triethylamine of condensation reaction And after the mixture of triethylamine hydrochloride carries out white picking, then hot blast film drying is carried out, the moisture of AKD products is down to Below 200ppm, acid number are down within 5ppm, finally enter product packaging systems.Comprise the following steps that：
Step 1：Pickling
A) 5% prefabricated hydrochloric acid is delivered to prefabricated salt acid storage tank, by the materials of AKD condensation reactions (AKD 55%, Triethylamine 11%, triethylamine hydrochloride 34%) by the pickling kettle of addition of AKD condensation reaction materials storage tank 1, while will be prefabricated 5% hydrochloric acid is added in a pickling kettle in salt acid storage tank, and the two occurs neutralization reaction and completes a pickling, obtains a pickling High-salt wastewater and a pickle containing thick AKD；
B) pickle containing thick AKD obtained in a) is squeezed into white picking kettle, is passed through 5% hydrochloric acid and carries out two Secondary washing, obtains moisture 0.8~1%, contains 45% 3 second obtained by the AKD crude products and white picking between acid number 15~20 The high-salt wastewater of amine hydrochlorate and 0.3%AKD products；
C) moisture 0.8~1% that will be obtained in b), the AKD crude products between acid number 15~20 squeeze into thick AKD storage tanks；
D) by the pickling high-salt wastewater obtained in a) and b) in obtain contain 45% triethylamine hydrochloride and 0.3% The white picking high-salt wastewater of AKD products squeezes into triethylamine hydrochloride storage tank；
It is described once or white picking kettle is for enamel still；
Step 2：Dehydration, depickling
By step 1c) in gained thick AKD storage tanks in AKD crude product (indexs：Moisture 0.8~1%；Acid number 15~ Between 20), be delivered in preheater after being preheated to 70~75 DEG C deliver into hot blast film drier 10 be dehydrated, depickling behaviour Make 30 minutes, its technological parameter operated is 120 DEG C of hot blast temperature, and air quantity is more than or equal to 200m3/ t, obtained AKD products enter Row physico-chemical analysis, moisture are less than 200ppm, and it is that qualified products deliver into AKD products granulation packaging system that acid number, which is less than 5ppm, Final be granulated is completed to pack；If moisture, acidity are unqualified, the operation of repeat step 2；
Described preheater is one kind in shell-and-tube, spiral heat exchanger in the prior art, hot blast film drier For coiled structure of the prior art；
Step 3：Triethylamine reclaims and wastewater treatment
A) by step 1d) in gained once, contain 45% triethylamine hydrochloride and 0.3%AKD products after white picking High-salt wastewater, through triethylamine hydrochloride storage tank be sent into triethylamine extraction kettle in, it is 10% sodium hydroxide to add excessive concentration Solution, it is sufficiently mixed, stands at 45 DEG C, being divided into two layers up and down；Upper oil phase is the triethylamine being obtained by extraction, lower floor's aqueous phase be containing 20%NaCl waste water；
B) triethylamine obtained in a) is sent into triethylamine refining kettle, while adds flaky sodium hydrate solid and taken off After water process, recycled；
C) waste water containing 20%NaCl obtained in a) is squeezed into sodium chloride high-salt wastewater storage tank, discharged after salt extraction is handled.
The present invention has advantages below：
1st, it is low-temperature operation, without coking, the purity of products obtained therefrom relative to traditional flash method AKD dewatering process, the present invention Height, colourity are good.
2nd, the present invention realizes aqueous AKD serialization dewatering process, and production capacity is high, and energy consumption is low, greatly reduces and is produced into This.
3rd, compared with traditional flash method AKD dewatering process, the technological operation can be by the part HCI in AKD with hydrochloric acid shape Formula steams, and the acid number of products obtained therefrom is significant lower, it is easy to (acid number is less than or equal to 5PPm) up to standard.
Brief description of the drawings
Fig. 1 is present invention process flow chart.
1-AKD condensation reaction material storage tanks；The prefabricated salt acid storage tanks of 2-；Pickling kettle of 3-；4- white picking kettles；5- is aqueous AKD storage tanks；6- triethylamine hydrochloride storage tanks；7- triethylamine extraction kettles；8- triethylamine refining kettles；9- sodium chloride high-salt wastewater stores up Groove；10- hot blast film driers；11- products are granulated packaging system；12- preheaters.
001- is condensed material；002-5% hydrochloric acid；The thick AKD of 003-；The aqueous AKD of 004-；005- watery hydrochloric acid；006- triethylamines Hydrochloric acid saline solution；007-10% sodium hydrate aqueous solutions；008-20% sodium chloride waste waters；009- flaky sodium hydrate solids； 010- reclaims triethylamine；011- sodium hydroxide lyes；012-AKD waste water；013- tiny structure systems.
01- hot blasts.
Embodiment
Describe the specific operation process of the present invention in detail with reference to the accompanying drawings and examples：
A kind of dewatering of AKD products, comprises the following steps：
Step 1：Pickling
A) 5% prefabricated hydrochloric acid is delivered to prefabricated salt acid storage tank 2, by the materials of AKD condensation reactions (AKD 55%, Triethylamine 11%, triethylamine hydrochloride 34%) by the pickling kettle 3 of addition of AKD condensation reaction materials storage tank 1, while will be pre- 5% hydrochloric acid is added in a pickling kettle 3 in salt manufacturing acid storage tank 2, and the two occurs neutralization reaction and completes a pickling, obtains once Pickling high-salt wastewater and a pickle containing thick AKD；
B) pickle containing thick AKD obtained in a) is squeezed into white picking kettle 4, is passed through the progress of 5% hydrochloric acid Secondary washing, obtains moisture 0.8~1%, contains 45% 3 obtained by the AKD crude products and white picking between acid number 15~20 The high-salt wastewater of ethylamine hydrochloride and 0.3%AKD products；
C) moisture 0.8~1% that will be obtained in b), the AKD crude products between acid number 15~20 squeeze into thick AKD storage tanks 5；
D) by the pickling high-salt wastewater obtained in a) and b) in obtain contain 45% triethylamine hydrochloride and 0.3% The white picking high-salt wastewater of AKD products squeezes into triethylamine hydrochloride storage tank 6；
Step 2：Dehydration, depickling
By step 1c) in gained thick AKD storage tanks 5 in AKD crude product (indexs：Moisture 0.8~1%；Acid number 15~ Between 20), be delivered to after being preheated to 70~75 DEG C in preheater 12 deliver into hot blast film drier 10 be dehydrated, depickling Operation, residence time are 30 minutes, and its technological parameter operated is 120 DEG C of hot blast temperature, and air quantity is more than or equal to 200m3/ t, AKD Moisture and micro HCL in crude product empty through tiny structure system 13；Obtained AKD products carry out physico-chemical analysis, and moisture is less than 200ppm, it is that qualified products deliver into AKD products granulation packaging system 11 that acid number, which is less than 5ppm, completes finally to be granulated packaging； If moisture, acidity are unqualified, the operation of repeat step 2；
Step 3：Triethylamine reclaims and wastewater treatment
A) by step 1d) in gained once, contain 45% triethylamine hydrochloride and 0.3%AKD products after white picking High-salt wastewater, be sent into through triethylamine hydrochloride storage tank 6 in triethylamine extraction kettle 7, it is 10% hydroxide to add excessive concentration Sodium solution, it is sufficiently mixed, stands at 45 DEG C, being divided into two layers up and down；Upper oil phase is the triethylamine being obtained by extraction, and lower floor's aqueous phase is Waste water containing 20%NaCI；
B) triethylamine obtained in a) is sent into triethylamine refining kettle 8, while adds the progress of flaky sodium hydrate solid After dewater treatment, recycled；
C) waste water containing 20%NaCI obtained in a) is squeezed into sodium chloride high-salt wastewater storage tank 9, discharged after salt extraction is handled.
Technological parameter and physico-chemical analysis result such as following table in each embodiment：
Show from upper table analysis of experiments result, as long as ensureing hot blast temperature at 120 DEG C, feeding temperature is 70 DEG C, during stop Between 30min, hot air flow is more than or equal to 200m3/ t can reach product quality requirement.

Claims (3)

  1. A kind of 1. dewatering of AKD products, it is characterised in that：AKD, triethylamine and the triethylamine hydrochloric acid of condensation reaction will be completed After the mixture of salt carries out white picking, then hot blast film drying is carried out, and triethylamine is recycled, specific steps are such as Under：
    Step 1：Pickling
    A) 5% prefabricated hydrochloric acid is delivered to prefabricated salt acid storage tank (2), by the material of AKD condensation reactions：AKD is 55wt%, Triethylamine 11wt%, triethylamine hydrochloride 34wt%, a pickling kettle (3) is added by AKD condensation reaction material storage tanks (1), 5% hydrochloric acid in prefabricated salt acid storage tank (2) is added in a pickling kettle (3) simultaneously, the two occurs neutralization reaction and completed once Pickling, obtain a pickling high-salt wastewater and a pickle containing thick AKD；
    B) pickle containing thick AKD obtained in a) is squeezed into white picking kettle (4), is passed through 5% hydrochloric acid and carries out two Secondary washing, obtains moisture 0.8~1%, contains 45% triethylamine salt obtained by the AKD crude products of acid number 15~20 and white picking The high-salt wastewater of hydrochlorate and 0.3%AKD products；
    C) moisture 0.8~1% that will be obtained in b), the AKD crude products between acid number 15~20 squeeze into thick AKD storage tanks (5)；
    D) by the pickling high-salt wastewater obtained in a) and b) in obtain produced containing 45% triethylamine hydrochloride and 0.3%AKD The white picking high-salt wastewater of product squeezes into triethylamine hydrochloride storage tank (6)；
    Step 2：Dehydration, depickling
    By the c of step 1) in gained thick AKD storage tanks (5) in AKD crude products, be delivered in preheater (12) and be preheated to 70~75 After DEG C, deliver into hot blast film drier (10) be dehydrated, depickling operate 30 minutes, 120 DEG C of hot blast temperature, air quantity >= 200m3/ t, obtained AKD products carry out physico-chemical analysis, and moisture is less than 200ppm, and acid number is qualified products less than 5ppm, conveying Packaging system (11) is granulated into AKD products, final be granulated is completed and packs；If moisture, acidity are unqualified, repeat step (2) Operation；
    Step 3：Triethylamine reclaims and wastewater treatment
    A) by the d of step 1) in gained once, after white picking containing 45% triethylamine hydrochloride and 0.3%AKD products High-salt wastewater, it is sent into through triethylamine hydrochloride storage tank (6) in triethylamine extraction kettle (7), it is 10% hydrogen-oxygen to add excessive concentration Change sodium solution, be sufficiently mixed, stand at 45 DEG C, being divided into two layers up and down；Upper oil phase is the triethylamine being obtained by extraction, lower floor's aqueous phase For waste water containing 20%NaCl；
    B) triethylamine obtained in a) is sent into triethylamine refining kettle (8), while adds flaky sodium hydrate solid and taken off After water process, recycled；
    C) waste water containing 20%NaCl obtained in a) is squeezed into sodium chloride high-salt wastewater storage tank (9), discharged after salt extraction is handled.
  2. A kind of 2. dewatering of AKD products as claimed in claim 1, it is characterised in that a described pickling kettle (3) or White picking kettle (4) is enamel still.
  3. 3. a kind of dewatering of AKD products as claimed in claim 1, it is characterised in that the preheater (12) is shell One kind in formula or spiral heat exchanger, hot blast film drier (10) are coiled structure.
CN201610008103.1A 2016-01-07 2016-01-07 A kind of method of AKD product dehydrates Expired - Fee Related CN105669601B (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0612739A1 (en) * 1993-02-22 1994-08-31 Eka Nobel Ab A process for the production of ketene dimers
WO2000034222A1 (en) * 1998-12-04 2000-06-15 Kemira Chemicals Oy Method for the manufacture of alkyl ketene dimers
CN101085739A (en) * 2007-07-04 2007-12-12 四川省乐山市福华农科投资集团有限责任公司 Dehydration treatment method for triethylamine
CN103864246A (en) * 2014-04-02 2014-06-18 青岛科技大学 Treatment method of effluent brine generated in alkyl ketene dimer production process
CN104478734A (en) * 2014-12-28 2015-04-01 甘肃银光聚银化工有限公司 Method for recycling crude product triethylamine in AKD (alkyl ketene dimer) production
CN104496941A (en) * 2014-12-29 2015-04-08 甘肃银光聚银化工有限公司 Method of continuously refining AKD mixture

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0612739A1 (en) * 1993-02-22 1994-08-31 Eka Nobel Ab A process for the production of ketene dimers
WO2000034222A1 (en) * 1998-12-04 2000-06-15 Kemira Chemicals Oy Method for the manufacture of alkyl ketene dimers
CN101085739A (en) * 2007-07-04 2007-12-12 四川省乐山市福华农科投资集团有限责任公司 Dehydration treatment method for triethylamine
CN103864246A (en) * 2014-04-02 2014-06-18 青岛科技大学 Treatment method of effluent brine generated in alkyl ketene dimer production process
CN104478734A (en) * 2014-12-28 2015-04-01 甘肃银光聚银化工有限公司 Method for recycling crude product triethylamine in AKD (alkyl ketene dimer) production
CN104496941A (en) * 2014-12-29 2015-04-08 甘肃银光聚银化工有限公司 Method of continuously refining AKD mixture

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