CN105668536A - Method of two-step production of II type ammonium polyphosphate - Google Patents
Method of two-step production of II type ammonium polyphosphate Download PDFInfo
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- CN105668536A CN105668536A CN201610029234.8A CN201610029234A CN105668536A CN 105668536 A CN105668536 A CN 105668536A CN 201610029234 A CN201610029234 A CN 201610029234A CN 105668536 A CN105668536 A CN 105668536A
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- ammonia
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/38—Condensed phosphates
- C01B25/40—Polyphosphates
- C01B25/405—Polyphosphates of ammonium
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Fireproofing Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention belongs to the field of inorganic chemical industry technology, and more specifically relates to a method of two-step production of II type ammonium polyphosphate. The method comprises the following steps: (1) liquefaction of a raw material yellow phosphorus; (2) the liquid yellow phosphorus is atomized in a spray gun by compressed air and is injected into a combustion furnace; (3) atomized yellow phosphorus combusts in the combustion furnace for generating phosphorus pentoxide gas; (4) the generated phosphorus pentoxide gas is cooled and enters a reactor; (4) a reaction is carried out between phosphorus pentoxide gas, ammonia gas and water in the reactor at a normal pressure, a white intermediate product is obtained, and the obtained white intermediate product is cooled and collected; (6) the collected white intermediate product is placed in polymerization equipment with ammonia gas added for heating polymerization; (7) a product after polymerization is grinded, and II type ammonium polyphosphate is obtained. The ammonium polyphosphate has the advantages of fine particles, white color, good dispersibility, good heat resistance, high crystallization II type purity, high polymerization degree, good quality, high safety in the whole production process, and large output.
Description
Technical field
The invention belongs to technical field of inorganic chemical industry, be specifically related to a kind of method that two steps produce II type APP.
Background technology
APP (APP) be a kind of efficiently, low toxicity, inexpensive inorganic combustion inhibitor, due to phosphorous, nitrogen quantity is high, resistance to water soak is strong, Heat stability is good, and proportion is little, and dispersive property is excellent, and product, can individually or use composite with other fire retardants close to neutral. It is widely used in the fire protection flame retarding of coating, plastics, paper, timber etc., it is possible to put out a fire for the large area in forest, coalfield etc. as dry powder extinguisher. As acid source in for expanding fire-proof paint, flame retardant effect is notable.
APP is a kind of important highly effective inorganic flame-proof agent, is a kind of unbranched polymer, and its general molecular formula is (NH4)n+2PnO3n+1, structural formula is
China starts development and production from the eighties in last century, is constantly in small scale, the situation that level is low. The producer that domestic production polyphosphoric acid is pressed is also few, and the product quality of its production differs, and the degree of polymerization of the APP of production is generally relatively low (n < 100), and yield is also smaller. The consumption of global fire retardant in 2009 is 152.6 ten thousand tons, and wherein, the consumption of phosphorus flame retardant is 28.0 ten thousand tons. Consumption to global fire retardant in 2014 increases 5%, is 194.5 ten thousand tons, and the consumption of phosphorus flame retardant increases 7.9%, reaches 40.9 ten thousand tons. APP, as a kind of important Phos flame retardant, is also the important component part constituting Intumescent Retardant System. When fire-retardant progressively from gas phase fire-retardant trend towards condensed phase fire-retardant, APP will become important growth point.
According to the scientific research that relevant polyphosphoric acid is pressed, the APP degree of polymerization produced at present is relatively low. And the industrialized production of high polymerization degree APP is to adopt phosphorus pentoxide system to produce, phosphorus pentoxide is high-risk chemical product, and human body is had serious harm. Therefore development safety in production high polymerization degree APP is extremely urgent.
Summary of the invention
The invention aims to solve the deficiencies in the prior art, it is provided that a kind of method that two steps produce II type APP, the present invention is achieved by the following technical solution:
A kind of method that two steps produce II type APP, including synthetic reaction and polyreaction, specifically comprises the following steps that
(1) raw material yellow phosphorus is liquefied;
(2) yellow phosphorus of post liquefaction being sent into spray gun, liquid phosphor sprays into combustion furnace after being atomized by compressed air in spray gun;
(3) yellow phosphorus being atomized burns in combustion furnace and generates phosphorus pentoxide gas, and the ignition temperature in combustion furnace is: 1000-2200 DEG C;
(4) the cooled device of phosphorus pentoxide gas generated in step (3) enters reactor after being cooled to 500-550 DEG C;
(5) the phosphorus pentoxide gas after cooling is obtained by reacting white intermediate product at ambient pressure with ammonia and water in the reactor, reaction temperature is 100-600 DEG C, phosphorus pentoxide: ammonia: water=(0.1-10): (1-5): 1, collects after the white intermediate product cooling obtained;
(6) white intermediate product collected being put into the logical ammonia of polymerization unit and adds thermal polymerization, temperature is 100-350 DEG C, and pressure is 0.05-1.5MPa, and polymerization time is: 0.5-20 hour;
(7) II type APP is obtained after being ground by the product of polyreaction;
Above step (1)-(5) are synthetic reaction, and step (6)-(7) are polyreaction.
Compression air in step (2) is once air after air compressor, moisture trap and measuring instrument.
Reactor described in step (4) is Wen's reactor.
Described white intermediate product is ammonium metaphosphate.
Described yellow phosphorus is industrial goods, and containing P >=99.9%, ammonia is that liquefied ammonia evaporation obtains, and liquefied ammonia is industrial goods, ammonia content >=99.9%, and water is deionized water.
The equipment that described polyreaction uses is special polyfurnace with pressure.
The mode of heating adopted in described polyreaction is the one of which of electrical heating, heat-conducting oil heating, superheated steam heating.
Compared with prior art, there is advantages that
The invention have the advantages that
1) APP that existing conventional method produces adopts phosphorus pentoxide system, and human body has serious injury, and the present invention adopts yellow phosphorus to produce nontoxic intermediate product, and repolymerization obtains APP, human body will not be had injury;
2) the APP phosphorus content that the present invention produces is big, nitrogen content is high, P2O5Content reaches as high as P2O574%; N content reaches as high as 14%, as fire retardant, has dehydration carbonization effect, and decomposes goes out incombustible nitrogen air-isolation and the covering to substrate surface of the polyphosphoric acid root, good flame retardation effect;
3) the APP degree of polymerization that the present invention produces is high and narrow molecular weight distribution, water solublity less than 0.5%, and fairly insoluble in common organic solvents, hygroscopicity is little, excellent for fireproof coating, powder extinguishing agent, plastic flame performance;
4) present invention produce APP grain is thin, color white, good dispersion, the feature that heat-resist, crystalline Form II purity is high;
5) the APP degree of polymerization that the present invention produces is high, and quality is good, and whole production process safety is high, and yield is big.
Accompanying drawing explanation
Fig. 1 is the diffracting spectrum of gained after the APP X diffraction analysis obtained by the embodiment of the present invention 1.
Detailed description of the invention
Embodiment 1
Through phosphorus spray gun, 3kg yellow phosphorus post liquefaction is sprayed into combustion furnace, and air is simultaneously entered phosphorus spray gun by air compressor after moisture trap and measuring instrument, under blast, is atomized by the liquid phosphorus of delivery nozzle, and at 1500 DEG C, burning generates gaseous state P2O5. Gaseous state P2O5Entering reactor reaction, ammonia and steam consumption respectively 1.6kg and 0.8kg with ammonia, steam after being water-cooled to 525 DEG C by cooling, reaction temperature is 400 DEG C, white intermediate product ammonium metaphosphate is obtained after reaction 30min, collecting after cooling, put in polymerization unit, logical ammonia adds thermal polymerization.Polymerization temperature is 220 DEG C, and gauge pressure is 0.7MPa, and rotating speed is 30r/min, reacts 2h, and cooling down product stops logical ammonia after 100 DEG C, obtains II type APP product after grinding.
The yellow phosphorus used in the present embodiment is industrial goods, and containing P >=99.9%, ammonia is that liquefied ammonia evaporation obtains, and liquefied ammonia is industrial goods, ammonia content >=99.9%, and water is deionized water. The equipment that polyreaction uses is special polyfurnace with pressure. The mode of heating adopted in polyreaction is electrical heating.
By the X diffraction analysis of the APP prepared by the present embodiment, analyze result and see that accompanying drawing 1, magnetic resonance detection average degree of polymerization are 1107.
Because the angle of diffraction is near 16 °, I-type APP is 3 diffraction maximums, and II-type APP is double diffraction peak; The angle of diffraction is between 20～23 °, and II-type APP has two diffraction maximums, and I-type APP does not have diffraction maximum, all occurs two obvious peaks as shown in Figure 1 near 16 ° and near 20 °, therefore this product is II type product.
Embodiment 2
Through phosphorus spray gun, 0.08kg yellow phosphorus post liquefaction is sprayed into combustion furnace, and air is simultaneously entered phosphorus spray gun by air compressor after moisture trap and measuring instrument, under blast, is atomized by the liquid phosphorus of delivery nozzle, and at 1000 DEG C, burning generates gaseous state P2O5. Entering reactor reaction, ammonia and steam consumption respectively 0.8kg and 0.8kg with ammonia, steam after being water-cooled to 500 DEG C by cooling, reaction temperature is 100 DEG C, white intermediate product ammonium metaphosphate is obtained after reaction 20min, collecting after cooling, put in polymerization unit, logical ammonia adds thermal polymerization. Polymerization temperature is 100 DEG C, and gauge pressure is 0.05MPa, and rotating speed is 30r/min, reacts 30min, and cooling down product stops logical ammonia after 100 DEG C, obtains II type APP product after grinding.
Yellow phosphorus in this enforcement is industrial goods, and containing P >=99.9%, ammonia is that liquefied ammonia evaporation obtains, and liquefied ammonia is industrial goods, ammonia content >=99.9%, and water is deionized water. The equipment that polyreaction uses is special polyfurnace with pressure. The mode of heating adopted in polyreaction is heat-conducting oil heating.
APP X diffraction analysis prepared by the present embodiment is II type product, and magnetic resonance detection average degree of polymerization is 783.
Embodiment 3
Through phosphorus spray gun, 30kg yellow phosphorus post liquefaction is sprayed into combustion furnace, and air is simultaneously entered phosphorus spray gun by air compressor after moisture trap and measuring instrument, under blast, is atomized by the liquid phosphorus of delivery nozzle, and at 2200 DEG C, burning generates gaseous state P2O5. Wen's reactor reaction is entered with ammonia, steam after being water-cooled to 550 DEG C by cooling, ammonia and steam consumption respectively 15kg and 3kg, reaction temperature is 600 DEG C, white intermediate product ammonium metaphosphate is obtained after reaction 20min, collect after cooling, putting in tailor-made polymer equipment, logical ammonia adds thermal polymerization. Polymerization temperature is 350 DEG C, and gauge pressure is 1.5MPa, and rotating speed is 30r/min, reacts 20h, and cooling down product stops logical ammonia after 100 DEG C, obtains II type APP product after grinding.
Yellow phosphorus in this enforcement is industrial goods, and containing P >=99.9%, ammonia is that liquefied ammonia evaporation obtains, and liquefied ammonia is industrial goods, ammonia content >=99.9%, and water is deionized water. The equipment that polyreaction uses is special polyfurnace with pressure. The mode of heating adopted in polyreaction is heat-conducting oil heating. Yellow phosphorus in this enforcement is industrial goods, and containing P >=99.9%, ammonia is that liquefied ammonia evaporation obtains, and liquefied ammonia is industrial goods, ammonia content >=99.9%, and water is deionized water.The equipment that polyreaction uses is special polyfurnace with pressure. The mode of heating adopted in polyreaction is superheated steam heating.
APP X diffraction analysis prepared by the present embodiment is II type product, and magnetic resonance detection average degree of polymerization is 843.
As follows with the II type APP indices contrast adopted obtained by existing technique by the II type APP obtained by the method for the present embodiment:
Table 1, the II type APP indices contrast table that distinct methods produces
| Contrast project | P2O5(%) | N(%) | The degree of polymerization | Water solublity (g/100ml water) | Flame retardant effect | Production process |
| The present embodiment | 74.71 | 14.27 | 1107 | 0.27 | UL94V-0 (20%APP+10% other fire retardants+70%PP) | Production process produces without disporduct |
| Phosphorus pentoxide system | ≥71 | ≥14 | ≥1000 | ≤0.5 | UL94V-0 (20%APP+10% other fire retardants+70%PP) | Raw material is phosphorus pentoxide, it is easy to human body is produced infringement 3--> |
| Other techniques | ≥69 | ≥14 | ≥50 | — | It is not used to plastic flame | I type APP with phosphoric acid, carbamide |
According to table 1 it can be seen that the II type APP product obtained by the present embodiment is at N, P2O5 content, the degree of polymerization, the II type APP all prepared slightly better than relatively phosphorus pentoxide system on dissolubility, can reach UL94V-0 rank for plastics (PP) are fire-retardant. And reaction is prepared ammonium metaphosphate by yellow phosphorus, repolymerization obtains APP, all nontoxic from intermediate product to finished product.
Claims (7)
1. the method that a step produces II type APP, it is characterised in that include synthetic reaction and polyreaction, specifically comprise the following steps that
(1) raw material yellow phosphorus is liquefied;
(2) yellow phosphorus of post liquefaction being sent into spray gun, liquid phosphor sprays into combustion furnace after being atomized by compressed air in spray gun;
(3) yellow phosphorus being atomized burns in combustion furnace and generates phosphorus pentoxide gas, and the ignition temperature in combustion furnace is: 1000-2200 DEG C;
(4) the cooled device of phosphorus pentoxide gas generated in step (3) enters reactor after being cooled to 500-550 DEG C;
(5) the phosphorus pentoxide gas after cooling is obtained by reacting white intermediate product at ambient pressure with ammonia and water in the reactor, reaction temperature is 100-600 DEG C, phosphorus pentoxide: ammonia: water=(0.1-10): (1-5): 1, collects after the white intermediate product cooling obtained;
(6) white intermediate product collected being put into the logical ammonia of polymerization unit and adds thermal polymerization, temperature is 100-350 DEG C, and pressure is 0.05-1.5MPa, and polymerization time is: 0.5-20 hour;
(7) II type APP is obtained after being ground by the product of polyreaction;
Above step (1)-(5) are synthetic reaction, and step (6)-(7) are polyreaction.
2. the method that a kind of two steps according to claim 1 produce II type APPs, it is characterised in that the compression air described in step (2) is once air after air compressor, moisture trap and measuring instrument.
3. the method that a kind of two steps according to claim 1 produce II type APP, it is characterised in that the reactor described in step (4) is Wen's reactor.
4. the method that a kind of two steps according to claim 1 produce II type APP, it is characterised in that described white intermediate product is ammonium metaphosphate.
5. the method that a kind of two steps according to claim 1 produce II type APP, it is characterised in that described yellow phosphorus is industrial goods, containing P >=99.9%, ammonia is that liquefied ammonia evaporation obtains, and liquefied ammonia is industrial goods, ammonia content >=99.9%, and water is deionized water.
6. the method that a kind of two steps according to claim 1 produce II type APP, it is characterised in that the equipment that described polyreaction uses is special polyfurnace with pressure.
7. the method that a kind of two steps according to claim 1 produce II type APP, it is characterised in that the mode of heating adopted in described polyreaction is the one of which of electrical heating, heat-conducting oil heating, superheated steam heating.
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| CN201610029234.8A CN105668536B (en) | 2016-01-18 | 2016-01-18 | A kind of method of two steps production II type APPs |
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| CN201610029234.8A CN105668536B (en) | 2016-01-18 | 2016-01-18 | A kind of method of two steps production II type APPs |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114314543A (en) * | 2021-12-10 | 2022-04-12 | 浙江彩蝶实业股份有限公司 | Synthesis process and application of phosphorus-nitrogen flame retardant |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1629070A (en) * | 2003-12-16 | 2005-06-22 | 浙江省化工研究院 | Method for preparing and detecting crystallization II type ammonium polyphosphate |
| CN1994873A (en) * | 2006-12-28 | 2007-07-11 | 四川大学 | Ammonium polyphosphate continuous production method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1629070A (en) * | 2003-12-16 | 2005-06-22 | 浙江省化工研究院 | Method for preparing and detecting crystallization II type ammonium polyphosphate |
| CN1994873A (en) * | 2006-12-28 | 2007-07-11 | 四川大学 | Ammonium polyphosphate continuous production method |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114314543A (en) * | 2021-12-10 | 2022-04-12 | 浙江彩蝶实业股份有限公司 | Synthesis process and application of phosphorus-nitrogen flame retardant |
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