CN104130285A - Continuous production process of 3-hydroxyphenyl phosphoroso-propanoic acid and production system thereof - Google Patents
Continuous production process of 3-hydroxyphenyl phosphoroso-propanoic acid and production system thereof Download PDFInfo
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- CN104130285A CN104130285A CN201410375748.XA CN201410375748A CN104130285A CN 104130285 A CN104130285 A CN 104130285A CN 201410375748 A CN201410375748 A CN 201410375748A CN 104130285 A CN104130285 A CN 104130285A
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Abstract
The invention discloses a continuous production process of 3-hydroxyphenyl phosphoroso-propanoic acid and a production system thereof. The production process includes synthesis, hydrolysis, primary crystallization, decolorization, secondary crystallization, drying and other steps. The production system is mainly composed of a synthesis kettle, a hydrolysis kettle, a first crystallization filtering mechanism, a decolorization kettle, a second crystallization filtering mechanism and a drying machine that are connected in order. The synthesis kettle is provided with a vacuum pumping port, a nitrogen inlet and a raw material storage tank. The hydrolysis kettle is provided with a first water storage tank and an HCl gas absorption device. The first crystallization filtering mechanism comprises a first crystallization groove, a first filter and a first filtrate groove that are connected in order. The first filtrate groove is internally provided with adsorption resin, and the discharge port of the first filtrate groove is connected to a resin regenerator. The decolorization kettle is connected to a second water storage tank and an activated carbon storage tank. The production process and the production system provided by the invention have the advantages of high product yield and purity, small wastewater emission, and low environmental pollution, etc.
Description
Technical field
The continuous production technology and the production system thereof that the present invention relates to a kind of 3-hydroxy phenyl phosphoroso-propionic acid, belong to chemical production field.
Background technology
Through the development of decades, flame-retarded technology has been obtained huge progress, and fire retardant is developed rapidly, and kind is increasing, and output grows steadily.At present, with regard to output and consumption, fire retardant has become the plastics additive that is only second to softening agent; And with regard to the annual growth of output, fire retardant occupies various plastics additives prostatitis.Fire retardant market has been a very active and energetic market.
Up to now, adopted fire retardant is various in style, according to different methods, has various classification.Different according to using method, fire retardant can be divided into addition type and the large class of response type two.Additive flame retardant is to add in the course of processing by after ignition resistant substrate moulding, with base material and other component, chemical reaction does not occur, and just with physics mode, is scattered in base material and forms flame retardant resistance, is used for thermal plasticity high polymer.Its technique is simpler, but easily affects processing, machinery and the application performance of material.In addition, due to compatibility problem, also there is " frosting " phenomenon in additive flame retardant, and the fire retardant being added in base material will ooze out after for some time, thereby reduce flame retardant properties.At present, additive flame retardant is still in occupation of the dominant position in fire retardant market.Reactive flame retardant adds in by ignition resistant substrate manufacturing processed, they or as the monomer of superpolymer, or as linking agent, participate in chemical reaction, finally become the structural unit of superpolymer and give high polymeric fire-retardant, be used for thermoset superpolymer.This method not only can make macromolecular material reach permanent fire-retardant, and does not substantially affect its excellent properties, but its maximum shortcoming is exactly often more complicated of preparation technology.
Phosphine oxide is the Organophosphorous compounds that a class is very stable, can be used as the fire retardant of polyester, polymeric amide etc., and obtained flame-retardant material color and luster is good, and mechanical property is good, and new variety are continuous in recent years.Especially the phosphinoxides fire retardant that contains reactive group in molecule, is the reactive flame retardant of a class excellent property, has consumption few, and flame retardant properties is good, fire-retardant lastingly, on being affected the advantages such as less by fire retardant material physical and mechanical properties.The good reactive flame retardant that can be used at present polyester is to take dichlorophenyl phosphine (DCPP) as basic derived product mostly, wherein 3-hydroxy phenyl phosphoroso-propionic acid (CEPPA) is that a class has higher thermostability, oxidative stability and good hydrolytic resistance, compared with the reactive flame retardant of the excellent property of high reaction activity.But the deficiency of its existence is: existing production technique and production unit be a large amount of industrial residue, the waste liquids of association in process of production, and environment is caused to serious pollution.
Summary of the invention
The object of this invention is to provide the continuous production technology of a kind of 3-hydroxy phenyl phosphoroso-propionic acid (CEPPA) and the production system matching with this production technique.
The present invention solves is the defects such as the productive rate that exists of existing 3-hydroxy phenyl phosphoroso-propionic acid (CEPPA) production technique and production system is low, environmental pollution is large.
The technical scheme that technical solution problem of the present invention adopts is: a kind of continuous production technology of 3-hydroxy phenyl phosphoroso-propionic acid, described production technique comprises the steps:
1) synthetic: the phenyl phosphorus dichloride of metering is dropped in reactor, and logical nitrogen protection, at 65～75 ℃, is added dropwise to reactor by the vinylformic acid of metering, in dropping process, keeps nitrogen protection, after being added dropwise to complete, insulation reaction for some time at 85～95 ℃;
2) hydrolysis: reaction mixture is added dropwise in the water of metering to the reaction that is hydrolyzed of 60 ℃ of left and right in hydrolysis kettle;
3) primary crystallization: after being hydrolyzed, by the crystallization of reaction solution cooling down, obtain 3-hydroxy phenyl phosphoroso-propionic acid crude product after crystal is filtered;
4) decolouring: crude product after primary crystallization is dropped in decolouring still to the water dissolution with 85～95 ℃, and add activated carbon decolorizing;
5) secondary crystal: remove by filter after gac, by the crystallization of reaction solution cooling down, and then filter crystal, can obtain 3-hydroxy phenyl phosphoroso-propionic acid fine work;
6) dry: crystal is placed in after dryer is dried and can obtains finished product.
Filtrate after filtering in described step 3 is recycled after renewable resin absorption again, and the recovery utilization rate of described renewable resin reaches more than 98%.
The chemical equation of above-mentioned production technique is as follows:
(1) building-up reactions
(2) hydrolysis reaction
A continuous production system for 3-hydroxy phenyl phosphoroso-propionic acid, described production system is mainly connected to form successively by synthesis reactor, hydrolysis kettle, the first crystallization filter mechanism, decolouring still, the second crystallization filter mechanism and dryer; The first raw material storage tank is connected with the opening for feed of synthesis reactor by the first volume pump, and the second raw material storage tank is connected with the opening for feed of synthesis reactor by the second volume pump; Described synthesis reactor is provided with vacuum orifice and nitrogen inlet; On described hydrolysis kettle, be connected with the first water storage tank and gas drain, on described gas drain, be connected with HCl gas absorbing device; Described the first crystallization filter mechanism is connected successively by the first crystallizer tank, the first strainer, the first filtrate receiver; The discharge port of described hydrolysis kettle is connected with the opening for feed of described the first crystallizer tank, and the liquid outlet opening of described the first strainer is connected with the first filtrate receiver, and the solid discharge port of described the first strainer is connected with the opening for feed of described decolouring still; In described the first filtrate receiver, be provided with polymeric adsorbent; The discharge port of described the first filtrate receiver is connected with resin regeneration device; On described decolouring still, be connected with the second water storage tank and gac storage tank; Described the second crystallization filter mechanism is connected with the second filtrate receiver successively by the second strainer, recrystallization groove, the 3rd strainer; The discharge port of described decolouring still is connected with the opening for feed of described the second strainer, and the liquid outlet opening of described the 3rd strainer is connected with the second filtrate receiver, and the solid discharge port of described the 3rd strainer is connected with dryer; In described synthesis reactor, hydrolysis kettle and decolouring still, be equipped with stirring rake.
Described HCl gas absorbing device is secondary water absorption unit.
The discharge port of the discharge port of described resin regeneration device and the second filtrate receiver is all connected with described hydrolysis kettle by the 3rd volume pump.
The invention has the beneficial effects as follows: compared with prior art, production technique provided by the invention and production system thereof, have the advantages such as the product yield of production is high, product purity is high, wastewater discharge is few, environmental pollution is low.
Accompanying drawing explanation
Fig. 1 is technological process of production schematic diagram of the present invention.
Fig. 2 is production equipment structural representation of the present invention.
Embodiment
Below in conjunction with drawings and Examples, the invention will be further described.
As shown in Figure 1, a kind of continuous production technology of 3-hydroxy phenyl phosphoroso-propionic acid, described production technique comprises the steps:
1) synthetic: 960 kg phenyl phosphorus dichlorides are dropped in reactor, and logical nitrogen protection, at 70 ℃, is added dropwise to reactor by 400 kg vinylformic acid, in dropping process, keeps nitrogen protection, after being added dropwise to complete, insulation reaction for some time at 90 ℃;
2) hydrolysis: reaction mixture is added dropwise in 220kg water to the reaction that is hydrolyzed of 60 ℃ of left and right in hydrolysis kettle;
3) primary crystallization: after being hydrolyzed, by the crystallization of reaction solution cooling down, obtain 3-hydroxy phenyl phosphoroso-propionic acid crude product after crystal is filtered; Filtrate after filtration is recycled after renewable resin absorption again, more energy-conserving and environment-protective;
4) decolouring: the crude product after primary crystallization is dropped in decolouring still and uses water dissolution, and add 40 kg activated carbon decolorizings;
5) secondary crystal: remove by filter after gac, by the crystallization of reaction solution cooling down, and then filter crystal, can obtain 3-hydroxy phenyl phosphoroso-propionic acid fine work;
6) dry: crystal to be placed in after dryer oven dry, to obtain 1123.1kg 3-hydroxy phenyl phosphoroso-propionic acid finished product.
In described production technique, in raw material phenyl phosphorus dichloride, building-up reactions rate is 99.5%; In building-up reactions thing, hydrolysis reaction rate is 100%, without side reaction, occurs; In raw material phenyl phosphorus dichloride, the final yield of 3-hydroxy phenyl phosphoroso-propionic acid finished product is 99.5%.
As shown in Figure 2, a kind of continuous production system of 3-hydroxy phenyl phosphoroso-propionic acid, described production system is mainly connected to form successively by synthesis reactor 1, hydrolysis kettle 11, the first crystallization filter mechanism, decolouring still 16, the second crystallization filter mechanism and dryer 23; The first raw material storage tank 4 is connected with the opening for feed of synthesis reactor 1 by the first volume pump 3, and the second raw material storage tank 5 is connected with the opening for feed of synthesis reactor 1 by the second volume pump 6; Described synthesis reactor 1 is provided with vacuum orifice 2 and nitrogen inlet 7; On described hydrolysis kettle 11, be connected with the first water storage tank 8 and gas drain 10, on described gas drain 10, be connected with HCl gas absorbing device 9; Described HCl gas absorbing device 9 is secondary water absorption unit.Described the first crystallization filter mechanism is connected successively by the first crystallizer tank 12, the first strainer 13, the first filtrate receiver 14; The discharge port of described hydrolysis kettle 11 is connected with the opening for feed of described the first crystallizer tank 12, and the liquid outlet opening of described the first strainer 13 is connected with the first filtrate receiver 14, and the solid discharge port of described the first strainer 13 is connected with the opening for feed of described decolouring still 16; In described the first filtrate receiver 14, be provided with polymeric adsorbent; The discharge port of described the first filtrate receiver 14 is connected with resin regeneration device 15; On described decolouring still 16, be connected with the second water storage tank 17 and gac storage tank 18; Described the second crystallization filter mechanism is connected successively by the second strainer 19, recrystallization groove 20, the 3rd strainer 21 and the second filtrate receiver 22; The discharge port of described decolouring still 16 is connected with the opening for feed of described the second strainer 19, and the liquid outlet opening of described the 3rd strainer 21 is connected with the second filtrate receiver 22, and the solid discharge port of described the 3rd strainer 21 is connected with dryer 23; The discharge port of the discharge port of described resin regeneration device 15 and the second filtrate receiver 22 is all connected with described hydrolysis kettle 11 by the 3rd volume pump 24, and the waste water after processing enters hydrolysis kettle 11 again for hydrolysis, realizes Matter Transfer utilization, has reduced wastewater discharge.In described synthesis reactor 1, hydrolysis kettle 11 and decolouring still 16, be equipped with stirring rake.
Claims (5)
1. the continuous production technology of a 3-hydroxy phenyl phosphoroso-propionic acid, it is characterized in that described production technique comprises the steps: 1) synthetic: the phenyl phosphorus dichloride of metering is dropped in reactor, logical nitrogen protection, at 65～75 ℃, the vinylformic acid of metering is added dropwise to reactor, in dropping process, keep nitrogen protection, after being added dropwise to complete, insulation reaction for some time at 85～95 ℃;
2) hydrolysis: reaction mixture is added dropwise in the water of metering to the reaction that is hydrolyzed of 60 ℃ of left and right in hydrolysis kettle;
3) primary crystallization: after being hydrolyzed, by the crystallization of reaction solution cooling down, obtain 3-hydroxy phenyl phosphoroso-propionic acid crude product after crystal is filtered;
4) decolouring: crude product after primary crystallization is dropped in decolouring still to the water dissolution with 85～95 ℃, and add activated carbon decolorizing;
5) secondary crystal: remove by filter after gac, by the crystallization of reaction solution cooling down, and then filter crystal, can obtain 3-hydroxy phenyl phosphoroso-propionic acid fine work;
6) dry: crystal is placed in after dryer is dried and can obtains finished product.
2. the continuous production technology of a kind of 3-hydroxy phenyl phosphoroso-propionic acid as claimed in claim 1, it is characterized in that in described step 3, the filtrate after filtration is recycled after renewable resin absorption again, the recovery utilization rate of described renewable resin reaches more than 98%.
3. a production system for the continuous production technology of 3-hydroxy phenyl phosphoroso-propionic acid as claimed in claim 1, is characterized in that described production system is mainly connected to form successively by synthesis reactor, hydrolysis kettle, the first crystallization filter mechanism, decolouring still, the second crystallization filter mechanism and dryer; The first raw material storage tank is connected with the opening for feed of synthesis reactor by the first volume pump, and the second raw material storage tank is connected with the opening for feed of synthesis reactor by the second volume pump; Described synthesis reactor is provided with vacuum orifice and nitrogen inlet; On described hydrolysis kettle, be connected with the first water storage tank and gas drain, on described gas drain, be connected with HCl gas absorbing device; Described the first crystallization filter mechanism is connected successively by the first crystallizer tank, the first strainer, the first filtrate receiver; The discharge port of described hydrolysis kettle is connected with the opening for feed of described the first crystallizer tank, and the liquid outlet opening of described the first strainer is connected with the first filtrate receiver, and the solid discharge port of described the first strainer is connected with the opening for feed of described decolouring still; In described the first filtrate receiver, be provided with polymeric adsorbent; The discharge port of described the first filtrate receiver is connected with resin regeneration device; On described decolouring still, be connected with the second water storage tank and gac storage tank; Described the second crystallization filter mechanism is connected with the second filtrate receiver successively by the second strainer, recrystallization groove, the 3rd strainer; The liquid outlet opening of described the 3rd strainer is connected with the second filtrate receiver, and the solid discharge port of described the 3rd strainer is connected with dryer; In described synthesis reactor, hydrolysis kettle and decolouring still, be equipped with stirring rake.
4. the continuous production system of a kind of 3-hydroxy phenyl phosphoroso-propionic acid as claimed in claim 3, is characterized in that described HCl gas absorbing device is secondary water absorption unit.
5. the continuous production system of a kind of 3-hydroxy phenyl phosphoroso-propionic acid as claimed in claim 3, is characterized in that the discharge port of described resin regeneration device and the discharge port of the second filtrate receiver are all connected with described hydrolysis kettle by the 3rd volume pump.
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Cited By (3)
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| CN105541908A (en) * | 2016-02-01 | 2016-05-04 | 东营美利达新型材料科技有限公司 | Method for producing 2-carboxethyl phenylphosphinic acid without wastewater |
| CN107376805A (en) * | 2017-08-14 | 2017-11-24 | 陕西昂煦生物科技有限公司 | A kind of matrine petroleum ether crystal system and its production technology |
| CN111659330A (en) * | 2020-04-23 | 2020-09-15 | 河北威远生物化工有限公司 | Process and equipment for continuously producing glufosinate-ammonium |
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| CN204039306U (en) * | 2014-08-01 | 2014-12-24 | 浙江阿尔法化工科技有限公司 | A kind of continuous production system of 3-hydroxy phenyl phosphoroso-propionic acid |
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| CN1300292A (en) * | 1999-02-19 | 2001-06-20 | 索罗蒂亚公司 | Preparation for 2-carboxyalkyl (phenyl) phosphoric acid |
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| CN105541908A (en) * | 2016-02-01 | 2016-05-04 | 东营美利达新型材料科技有限公司 | Method for producing 2-carboxethyl phenylphosphinic acid without wastewater |
| CN107376805A (en) * | 2017-08-14 | 2017-11-24 | 陕西昂煦生物科技有限公司 | A kind of matrine petroleum ether crystal system and its production technology |
| CN111659330A (en) * | 2020-04-23 | 2020-09-15 | 河北威远生物化工有限公司 | Process and equipment for continuously producing glufosinate-ammonium |
| CN111659330B (en) * | 2020-04-23 | 2021-05-07 | 河北威远生物化工有限公司 | Process and equipment for continuously producing glufosinate-ammonium |
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Application publication date: 20141105 |