CN110240495A - A kind of method of caprolactam and phosphoric acid coproducing ammonium - Google Patents
A kind of method of caprolactam and phosphoric acid coproducing ammonium Download PDFInfo
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- CN110240495A CN110240495A CN201910641111.3A CN201910641111A CN110240495A CN 110240495 A CN110240495 A CN 110240495A CN 201910641111 A CN201910641111 A CN 201910641111A CN 110240495 A CN110240495 A CN 110240495A
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05B—PHOSPHATIC FERTILISERS
- C05B7/00—Fertilisers based essentially on alkali or ammonium orthophosphates
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D223/00—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom
- C07D223/02—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings
- C07D223/06—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D223/08—Oxygen atoms
- C07D223/10—Oxygen atoms attached in position 2
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Abstract
The present invention relates to the fields that coproduction prepares caprolactam and ammonium phosphate, disclose the method for a kind of caprolactam and phosphoric acid coproducing ammonium.This method comprises: (1) carries out caprolactam sulfuric ester and the slurries containing rock phosphate in powder that caprolactam phosphate aqueous solution is obtained by extraction；(2) the caprolactam phosphate aqueous solution and ammonia injection are loaded in the reactor of ammonium phosphate mother liquor and carry out neutralization reaction.The higher caprolactam of yield and purity and ammonium phosphate, great prospects for commercial application can be obtained using this method simultaneously.
Description
Technical field
The present invention relates to the preparation field of caprolactam and phosphoric acid coproducing ammonium, a kind of caprolactam and ammonium phosphate connection are disclosed
The method of production.
Background technique
Ammonium phosphate described in this specification includes monoammonium phosphate (Ammonium Diacidphosphate) and Diammonium phosphate (DAP)
(Diammonium Phosphate), inorganic compound, molecular formula are respectively (NH4)H2PO4(NH4)2HPO4, it is the ammonium of phosphoric acid
Salt, there are anhydrides and hydrate.Monoammonium phosphate and Diammonium phosphate (DAP) are clear crystal or pale powder, are sometimes particle, easily
It is dissolved in water.Ammonium phosphate contains nitrogen, phosphorus, is a kind of compound fertilizer.
The molecular formula of caprolactam is C6H11NO, appearance are white powder or crystalline solid, there is oiliness feel.Caprolactam is
One of important Organic Chemicals is mainly used for production polycaprolactam, and the latter about 90% is for producing synthetic fibers, i.e.,
Caprone, 10% is used as plastics, for manufacturing gear, bearing, tubing, medical instrument and electrical, insulating materials etc..It is also used for applying
Material, plastic agent and marginally for synthetic lysine etc..Currently, the preparation method of caprolactam mainly has (1) phynol method；(2)
Cyclohexane oxidation process；(3) toluene method.
Byproduct of ammonium sulfate can be nearly all generated in the production method of caprolactam at present.Byproduct of ammonium sulfate, being will be high
The liquefied ammonia and oleum of price are converted into the ammonium sulfate of low price, therefore the ammonium sulfate of by-product is higher, and cost is higher.Not only
In this way, a kind of nitrogen fertilizer of the ammonium sulfate as inefficient and aobvious acidity, unwelcome always, the ammonium sulfate of by-product is excessively high, also deposits
The sales difficulty the problem of.
Therefore, a kind of method for researching and developing coproduction caprolactam and ammonium phosphate is of great significance.
Summary of the invention
The purpose of the invention is to overcome, there are byproduct sulphur in the preparation method of caprolactam of the existing technology
The defect problem of sour ammonium, provides the method for a kind of caprolactam and phosphoric acid coproducing ammonium, can obtain yield simultaneously using this method
With the higher caprolactam of purity and ammonium phosphate, and this method can be realized the target of not producing ammonium sulfate byproduct, and great industry is answered
Use prospect.
To achieve the goals above, the present invention provides a kind of methods of caprolactam and phosphoric acid coproducing ammonium, wherein the party
Method includes:
(1) it carries out caprolactam sulfuric ester and the slurries containing rock phosphate in powder that caprolactam phosphate aqueous solution is obtained by extraction；
(2) the caprolactam phosphate aqueous solution and ammonia injection are loaded in the reactor of ammonium phosphate mother liquor and are neutralized
Reaction.
The present inventor has found after study, reacts caprolactam sulfuric ester and rock phosphate in powder to obtain calcium sulfate and oneself
Lactams phosphoric acid, the caprolactam phosphate aqueous solution and ammonia that will separate calcium sulfate carry out neutralization reaction, available acyl in oneself
Amine and ammonium phosphate, to realize the target of not producing ammonium sulfate byproduct, great prospects for commercial application.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 is the signal of a kind of coproduction caprolactam of specific embodiment according to the present invention and the method for ammonium phosphate
Figure.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
A kind of method of caprolactam and phosphoric acid coproducing ammonium provided by the invention, wherein this method comprises:
(1) it carries out caprolactam sulfuric ester and the slurries containing rock phosphate in powder that caprolactam phosphate aqueous solution is obtained by extraction；
(2) the caprolactam phosphate aqueous solution and ammonia injection are loaded in the reactor of ammonium phosphate mother liquor and are neutralized
Reaction.
According to the present invention, in step (1), the rock phosphate in powder contain one of phosphorus, calcium, fluorine, silicon, iron, magnesium and aluminium or
It is a variety of；Preferably, on the basis of the total weight of the rock phosphate in powder, the content of P elements presses P2O5It is calculated as 28-33 weight %；It is described
The average grain diameter of rock phosphate in powder can be 0.01-2mm；In addition, rock phosphate in powder can be commercially available, for example, Hubei can be purchased from
Three peaceful model SN001；And the content of each component is respectively P elements (with P in the rock phosphate in powder2O5Meter) it is 25%-35%,
Calcium constituent (in terms of CaO) is 30%-50%, and magnesium elements (in terms of MgO) are 1%-10%, and ferro element is (with Fe2O3Meter) it is 1%-
3%, aluminium element is (with Al2O3Meter) it is 1%-8%, element silicon is (with SiO2Meter) 5%-15% is, fluorine element (in terms of F) is 1%-
5%.In addition, in the present invention, rock phosphate in powder can be dissolved in the water to obtain by the slurries containing rock phosphate in powder.
According to the present invention, sulfuric acid content can be 50-60 weight %, SO in the caprolactam sulfuric ester3Content can be with
For 4-10 weight %.
According to the present invention, the molar ratio of the dosage of the caprolactam sulfuric ester and the rock phosphate in powder can be (10-1):
1, preferably (4-5): 1.In the present invention, by the dosage of caprolactam sulfuric ester and the rock phosphate in powder control for above range it
It is interior, it can make full use of the sulfuric acid in caprolactam sulfuric ester, while improving the yield of phosphoric acid.
According to the present invention, in step (1), the condition of the extraction includes: that temperature can be 83-100 DEG C, extracting pressure
Can be between 96-99KPa in absolute pressure, the time can be 0.5-8 hours；It is 83-95 DEG C in temperature under preferable case,
Time is 3-5 hours, and when absolute pressure is 98KPa, effect is more preferable.
According to the present invention, the ammonia can be injected in the form of ammonia, can also be injected in the form of ammonium hydroxide.When with ammonium hydroxide
When form is injected, the concentration of the ammonium hydroxide is preferably 10-30 weight %.Under preferable case, the ammonia is injected in the form of ammonia,
The crystallization that avoid constantly water is introduced into reaction system, can be more advantageous to ammonium phosphate in this way is precipitated.
The present invention is not particularly limited the dosage of the caprolactam sulfuric ester and ammonia, as long as oneself can be generated simultaneously
Lactams and ammonium phosphate, but in order to improve the utilization rate of raw material, on the basis of the caprolactam sulfuric ester of 1mol, the ammonia
Dosage be preferably 1-3mol.It should be noted that working as ammonia in the form of ammonium hydroxide in use, the dosage of ammonia described herein is not wrapped
Include the content of water.
According to the present invention, usually, the neutralization reaction includes the temperature of reaction, the pressure of reaction, the pH value of reaction
And the time of reaction, in the present invention, in order to be more advantageous to the progress of neutralization reaction, the temperature of the reaction can be 60-
100 DEG C, the pH of reaction can be 4-8, and the absolute pressure of the reaction can be 16-140KPa, in addition, the extension in reaction time
Be conducive to the raising of reaction-ure conversion-age and reaction product yield, but the reaction time is too long to reaction-ure conversion-age and reaction
The amplitude that product yield improves is not obvious, and therefore, comprehensively considers effect and efficiency, the time of the reaction is preferably 1-10 small
When.After reaction, caprolactam is easy to separate with the ammonium phosphate mother liquor as heavy phase as light phase, and is sent into subsequent purification work
In sequence, such as extracting and refining, finished product caprolactam is made；And ammonium phosphate mother liquor then by among the above with generate under reaction condition
Neutralization reaction heat under the action of continuous evaporation and concentrating, reach saturation state, in the form of ammonium phosphate crystal be precipitated, and by from
The subsequent processings such as the heart, dehydration, drying obtain the packaging export trade of finished product ammonium phosphate.
According to the present invention, the concentration of the caprolactam phosphate aqueous solution is 20-80 weight %, preferably 40-70 weight
Measure %；In the present invention, the concentration of the caprolactam phosphate aqueous solution is controlled as within above range, advantage is to save to steam
Vapour consumes and is easy to caprolactam and ammonium phosphate solution split-phase.
According to the present invention, the ammonium phosphate mother liquor is the aqueous solution of ammonium phosphate.The present invention is to the ammonium phosphate mother liquor
Concentration is not particularly limited, as long as can slow down the severe degree of neutralization reaction and the crystallization for product ammonium phosphate provides nucleus
, for example, the concentration of the ammonium phosphate mother liquor can be 10-40 weight %, preferably 20-30 weight %.
According to the present invention, the dosage of the ammonium phosphate mother liquor usually can reasonably be selected according to the size of reactor
It selects.Under preferable case, the splendid attire liquid level of the ammonium phosphate mother liquor accounts for the 20-50% of the reactor storage liquid level,
It on the one hand can guarantee that the ammonium phosphate generated can sufficiently be precipitated in this way, on the other hand can guarantee that the caprolactam generated can
It is easily separated with the ammonium phosphate heavy phase of generation by overflow as light phase.
The method of caprolactam and phosphoric acid coproducing ammonium provided by the invention further preferably includes preparing in oneself in accordance with the following methods
The step of amido sulfuric acid ester: in the presence of oleum, cyclohexanone oxime is subjected to Beckmann rearrangement.
Wherein, in the presence of oleum, cyclohexanone oxime is subjected to Beckmann rearrangement to prepare caprolactam sulfuric ester
Reaction process be known to the skilled person, specific reaction is as follows:
The oleum refers to the sulfuric acid solution well known to a person skilled in the art sulfur trioxide.
According to the present invention, the condition of the Beckmann rearrangement can be the conventional selection of this field, generally include anti-
The time of the temperature and reaction answered.The temperature of the reaction for example can be 85-130 DEG C, and the time of the reaction for example can be with
It is 0.1-2 hours.Under preferable case, the temperature of the reaction is 90-120 DEG C, and the time of the reaction is 0.5-1 hours.
Further, when the ammonia is injected in the form of ammonia, reduce the introducing of water, can be avoided reacting in this way
After, excessive water passes through energy consumption caused by steam heating evaporation, is beneficial to energy conservation.
According to the present invention, the neutralization reaction can carry out in existing various reactors, divide preferably in crystallization
It is carried out from device.The crystal separator preferably includes multiple caprolactam phosphate aqueous solution entrances and (is commonly called as caprolactam phosphoric acid
Ester nozzle) and multiple ammonia entrances (being commonly called as ammonia nozzle).The quantity of the caprolactam phosphate entrance and ammonia entrance can basis
Actual conditions are reasonably selected, for example, 2-6 can be respectively.It is further preferred that multiple caprolactam phosphates enter
Mouth is identical as the quantity of multiple ammonia entrances；It is highly preferred that multiple caprolactam phosphate entrances are alternately arranged with multiple ammonia entrances,
It enables to material to more uniformly spread in this way and reduces the generation of side reaction.
In addition, the method for caprolactam provided by the invention and phosphoric acid coproducing ammonium further include neutralization reaction completion after,
By obtained product by sedimentation separation, to obtain the light phase (oily phase) containing caprolactam and the heavy phase (water containing ammonium phosphate
Phase).Further, the light phase containing caprolactam is sent into subsequent refining step and is refined.And contain ammonium phosphate
Heavy phase is then 60-100 DEG C, pH=4-8, absolute pressure 16-140KPa, time 1- in temperature under the action of neutralization reaction heat
It is evaporated concentrate under conditions of 10 hours, then send into centrifuge obtained concentrate product to drying and dehydrating, finished product is made
Ammonium phosphate packs export trade.The method of the purification is known to the skilled person, and will not be described in great detail herein.In addition, in this hair
It is 65-90 DEG C, pH=4-7, absolute pressure 20-100KPa in temperature under preferable case in bright, the condition of time 1-5 hour
Under be evaporated concentrate；It is 70-80 DEG C, pH=4-6, absolute pressure 20-30KPa, time 1- in temperature in more preferable situation
Concentrate is evaporated under conditions of 3 hours.
According to the present invention, as shown in Figure 1, the method for caprolactam provided by the invention and phosphoric acid coproducing ammonium is included in smoke
In the presence of sulfuric acid (concentrated sulfuric acid), cyclohexanone oxime is subjected to Beckmann rearrangement, obtains the production containing caprolactam sulfuric ester
Object reacts caprolactam sulfuric ester and rock phosphate in powder to obtain calcium sulfate and caprolactam phosphoric acid, by separate calcium sulfate oneself in
Amidophosphoric acid aqueous solution and ammonia are passed through in the neutralization crystal separator equipped with ammonium phosphate mother liquor simultaneously carries out neutralization reaction.It neutralizes
After reaction is completed, by obtained product by sedimentation separation, to obtain the light phase containing caprolactam and containing ammonium phosphate
Heavy phase.Then the light phase containing caprolactam is sent into subsequent refining step again and is refined, obtain finished product caprolactam.
And the heavy phase containing ammonium phosphate is then evaporated concentrate in the presence of neutralization reaction heat, then by obtained concentrate product send to from
Drying and dehydrating in scheming obtains finished product ammonium phosphate.
The present invention will be described in detail by way of examples below.
In following embodiment and comparative example:
The concentration of caprolactam and the purity of ammonium phosphate are all made of the high performance liquid chromatograph purchased from Japanese Shimadzu Corporation
It is measured.
The yield of caprolactam and the yield of ammonium phosphate are calculated by using the following formula:
The yield of caprolactam=(concentration × light phase weight of caprolactam in light phase) ÷ caprolactam is theoretical to be produced
Amount × 100%；
The yield of ammonium phosphate=(purity × weight of ammonium phosphate in product) ÷ ammonium phosphate theoretical yield × 100%.
Embodiment 1
The embodiment is used to illustrate the preparation method of caprolactam and phosphoric acid coproducing ammonium provided by the invention.
(1) preparation of caprolactam sulfuric ester
(wherein, sulfuric acid content is 80 weight % to the oleum for being 20 weight % by cyclohexanone oxime and concentration, and dissociate SO3
Content be 20 weight %) be uniformly mixed according to the ratio of molar ratio 1:1.5, obtain circulation rearrangement solution, then the circulation reset
The temperature of liquid, which is introduced into reset in mixer after rising to 100 DEG C, reacts 1 hour, obtains the solution containing caprolactam sulfuric ester.
(2) coproduction of caprolactam and ammonium phosphate
It takes 100g caprolactam sulfuric ester to be added in 1L beaker, while 100g rock phosphate in powder slurries is added into beaker and (contain
Admittedly measuring 60%) with 200g acid reflux (acid reflux is to wash the wash water of ardealite), at a temperature of 86 DEG C, extracting pressure is in absolute pressure
React 30min under 98KPa, reaction slurry filtered with vacuum pump, with 100g water washing three times after, caprolactam contains in ardealite
Measuring (mass percent) is 0.0046%；Wherein, on the basis of the total weight of the rock phosphate in powder, the content of P elements presses P2O5Meter
For 28 weight %；And the average grain diameter of rock phosphate in powder is 1mm；Sulfuric acid content is 50 weight %, SO in caprolactam sulfuric ester3Contain
Amount is 10 weight %.
Compound concentration is the ammonium phosphate mother liquor of 20 weight % in advance in and in crystal separator, contains liquid level control
It is made as neutralizing the 40% of crystal separator storage liquid level.Neutralizing crystal separator includes four caprolactam phosphate nozzles
With four ammonia nozzles, four caprolactam phosphate nozzles and four ammonia nozzles are alternately arranged.
Ammonium hydroxide is added into the filtrate (caprolactam phosphate aqueous solution) separated after ardealite, wherein containing in oneself
Amidophosphoric acid aqueous solution and ammonia are passed through neutralization crystal separator by respective special nozzle respectively.Control caprolactam phosphoric acid water
Flow containing caprolactam phosphate aqueous solution in wash nozzle is 7.88m3/ h, ammonia flow is 3130Nm in ammonia nozzle3/
h.Maintain liquid level of the reaction solution in and in crystal separator be in and crystal separator storage liquid level it is 40% left
The right side, and control the temperature neutralized in crystal separator and be stirred to react the time for 70 DEG C, pH=4.5, absolute pressure 25KPa
Material after reaction is centrifugated by 60min with centrifuge, and supernatant liquid obtains caprolactam after extracting, refining
44.7g, through analytical control, which meets GB/T 13254-2017 high-class product standard；Lower layer's heavy phase passes through evaporation and concentrating
Finished product ammonium phosphate is made, total nutrient is (with N+P2O5Meter, mass percentage) 55% or so.
Embodiment 2
The embodiment is used to illustrate the preparation method of caprolactam and phosphoric acid coproducing ammonium provided by the invention.
(1) preparation of caprolactam sulfuric ester
It is same as Example 1.
(2) coproduction of caprolactam and ammonium phosphate
It takes 100g caprolactam sulfuric ester to be added in 1L beaker, while 200g rock phosphate in powder slurries is added into beaker and (contain
Admittedly measuring 60%) with 200g acid reflux (acid reflux is to wash the wash water of ardealite), at a temperature of 86 DEG C, extracting pressure is in absolute pressure
React 60min under 96KPa, reaction slurry filtered with vacuum pump, with 100g water washing three times after, caprolactam contains in ardealite
Measuring (mass percent) is 0.0006%；Wherein, on the basis of the total weight of the rock phosphate in powder, the content of P elements presses P2O5Meter
For 33 weight %；And the average grain diameter of rock phosphate in powder is 0.01mm；Sulfuric acid content is 60 weight % in caprolactam sulfuric ester,
SO3Content is 4 weight %.
Compound concentration is the ammonium phosphate mother liquor of 20 weight % in advance in and in crystal separator, contains liquid level control
It is made as neutralizing the 40% of crystal separator storage liquid level.Neutralizing crystal separator includes four caprolactam phosphate nozzles
With four ammonia nozzles, four caprolactam phosphate nozzles and four ammonia nozzles are alternately arranged.
To the filtrate caprolactam phosphate aqueous solution separated after ardealite) in ammonium hydroxide is added, wherein contain acyl in oneself
Amine phosphate aqueous solution and ammonia are passed through neutralization crystal separator by respective special nozzle respectively.It is water-soluble to control caprolactam phosphoric acid
Flow containing caprolactam phosphate aqueous solution in nozzle for liquid is 12.89m3/ h, ammonia flow is 5329Nm in ammonia nozzle3/h。
Liquid level of the maintenance reaction solution in and in crystal separator stores 40% or so of liquid level with crystal separator in being,
And 75 DEG C of reaction temperature neutralized in crystal separator are controlled, pH=4, absolute pressure 20kPa are stirred to react time 60min,
Material after reaction is centrifugated with centrifuge, supernatant liquid obtains caprolactam 44.9g after extracting, refining, through dividing
Analysis is examined, which meets GB/T 13254-2017 high-class product standard；Finished product phosphorus is made by evaporation and concentrating in lower layer's heavy phase
Sour ammonium, total nutrient is (with N+P2O5Meter, mass percentage) 55% or so.
Embodiment 3
The embodiment is used to illustrate the preparation method of caprolactam and phosphoric acid coproducing ammonium provided by the invention.
(1) preparation of caprolactam sulfuric ester
It is same as Example 1.
(2) coproduction of caprolactam and ammonium phosphate
It takes 100g caprolactam sulfuric ester to be added in 1L beaker, while 100g rock phosphate in powder slurries is added into beaker and (contain
Admittedly measuring 60%) with 200g acid reflux (acid reflux is to wash the wash water of ardealite), at a temperature of 86 DEG C, extracting pressure is in absolute pressure
React 60min under 97KPa, reaction slurry filtered with vacuum pump, with 100g water washing three times after, caprolactam contains in ardealite
Measuring (mass percent) is 0.0036%；Wherein, on the basis of the total weight of the rock phosphate in powder, the content of P elements presses P2O5Meter
For 30 weight %；And the average grain diameter of rock phosphate in powder is 2mm；Sulfuric acid content is 55 weight %, SO in caprolactam sulfuric ester3Contain
Amount is 8 weight %.
Compound concentration is the ammonium phosphate mother liquor of 20 weight % in advance in and in crystal separator, contains liquid level control
It is made as neutralizing the 40% of crystal separator storage liquid level.Neutralizing crystal separator includes four caprolactam phosphate nozzles
With four ammonia nozzles, four caprolactam phosphate nozzles and four ammonia nozzles are alternately arranged.
Ammonium hydroxide is added into the filtrate (caprolactam phosphate aqueous solution) separated after ardealite, wherein containing in oneself
Amidophosphoric acid aqueous solution and ammonia are passed through neutralization crystal separator by respective special nozzle respectively.Control caprolactam phosphoric acid water
Flow containing caprolactam phosphate aqueous solution in wash nozzle is 18.32m3/ h, ammonia flow is 7501Nm in ammonia nozzle3/
h.Maintain liquid level of the reaction solution in and in crystal separator be in and crystal separator storage liquid level it is 40% left
The right side, and control the temperature neutralized in crystal separator and be stirred to react the time for 75 DEG C, pH=5, absolute pressure 30kPa
Material after reaction is centrifugated by 60min with centrifuge, and supernatant liquid obtains caprolactam after extracting, refining
44.7g, through analytical control, which meets GB/T 13254-2017 high-class product standard；Lower layer's heavy phase passes through evaporation and concentrating
Finished product ammonium phosphate is made, total nutrient is (with N+P2O5Meter, mass percentage) 55% or so.
Embodiment 4
The embodiment is used to illustrate the preparation method of caprolactam and phosphoric acid coproducing ammonium provided by the invention.
According to the method for embodiment 1 carry out caprolactam and ammonium phosphate coproduction, institute the difference is that:
It takes 100g caprolactam sulfuric ester to be added in 1L beaker, while 200g rock phosphate in powder slurries is added into beaker and (contain
Admittedly measuring 60%) with 200g acid reflux (acid reflux is to wash the wash water of ardealite), at a temperature of 86 DEG C, extracting pressure is absolute pressure
React 120min under 99KPa, reaction slurry filtered with vacuum pump, with 100g water washing three times after, caprolactam in ardealite
Content (mass percent) is 0.0003%；Wherein, on the basis of the total weight of the rock phosphate in powder, the content of P elements presses P2O5
It is calculated as 32 weight %；And the average grain diameter of rock phosphate in powder is 1mm；Sulfuric acid content is 52 weight %, SO in caprolactam sulfuric ester3
Content is 6 weight %.
Compound concentration is the ammonium phosphate mother liquor of 20 weight % in advance in and in crystal separator, contains liquid level control
It is made as neutralizing the 40% of crystal separator storage liquid level.Neutralizing crystal separator includes four caprolactam phosphate nozzles
With four ammonia nozzles, four caprolactam phosphate nozzles and four ammonia nozzles are alternately arranged.
Ammonium hydroxide is added into the filtrate separated after ardealite, controls 75 DEG C of reaction temperature, pH=5, absolute pressure is
26kPa is stirred to react time 60min, and the material after reaction is centrifugated with centrifuge, and supernatant liquid is by extraction, purification
After obtain caprolactam 44.9g, through analytical control, which meets GB/T 13254-2017 high-class product standard；Lower layer's weight
Finished product ammonium phosphate mutually is made by evaporation and concentrating, total nutrient is (with N+P2O5Meter, mass percentage) 55% or so.
Comparative example 1
The method that the comparative example is used to illustrate the caprolactam and sulfuric acid coproducing ammonium of reference.
The coproduction of caprolactam and ammonium phosphate is carried out according to the method for embodiment 1, unlike, not by caprolactam sulphur
Acid esters and the slurries containing rock phosphate in powder carry out that caprolactam phosphate aqueous solution is obtained by extraction；But it will directly contain caprolactam sulphur
The solution and ammonia of acid esters pass through respective special nozzle respectively and are passed through in neutralization crystal separator, wherein neutralize crystal separator
In do not prestore concentration be 20 weight % ammonium phosphate mother liquor.Stop reaction after reaction 4 hours, reaction product is passed through into sedimentation point
From, obtain the light phase containing caprolactam and the heavy phase containing ammonium phosphate, still, have by-product ammonium sulfate generation.
As can be seen from the above results, the coproduction of caprolactam and ammonium phosphate, energy are carried out using method provided by the invention
Enough while the higher caprolactam of yield and purity and ammonium phosphate are obtained, and is generated without byproduct of ammonium sulfate.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (10)
1. a kind of method of caprolactam and phosphoric acid coproducing ammonium, which is characterized in that this method comprises:
(1) it carries out caprolactam sulfuric ester and the slurries containing rock phosphate in powder that caprolactam phosphate aqueous solution is obtained by extraction；
(2) the caprolactam phosphate aqueous solution and ammonia injection are loaded in the reactor of ammonium phosphate mother liquor and neutralize instead
It answers.
2. according to the method described in claim 1, wherein, in step (1), the rock phosphate in powder contain phosphorus, calcium, fluorine, silicon, iron,
One of magnesium and aluminium are a variety of；
Preferably, on the basis of the total weight of the rock phosphate in powder, the content of P elements presses P2O5It is calculated as 28-33 weight %；
Preferably, the average grain diameter of the rock phosphate in powder is 0.01-2mm.
3. method according to claim 1 or 2, wherein sulfuric acid content is 50-60 weight in the caprolactam sulfuric ester
Measure %, SO3Content is 4-10 weight %.
4. according to the method described in claim 1, wherein, mole of the dosage of the caprolactam sulfuric ester and the rock phosphate in powder
Than for (10-1): 1.
5. according to the method described in claim 1, wherein, in step (1), the condition of the extraction includes: that temperature is 83-
100 DEG C, absolute pressure 96-99KPa, the time is 0.5-8 hours.
6. according to the method described in claim 1, wherein, in step (2), the ammonia is injected in the form of ammonia or ammonium hydroxide,
Preferably ammonia.
7. method according to claim 1 or 6, wherein on the basis of the caprolactam sulfuric ester of 1mol, the use of the ammonia
Amount is 1-3mol.
8. according to the method described in claim 1, wherein, in step (2), the condition of the neutralization reaction includes: that temperature is
60-100 DEG C, pH 4-8, absolute pressure 16-140KPa, the time is 1-10 hours.
9. according to the method described in claim 1, wherein, the concentration of the caprolactam phosphate aqueous solution is 20-80 weight %；
Preferably, the concentration of the ammonium phosphate mother liquor is 10-40 weight %.
10. according to the method described in claim 1, wherein, this method further includes preparing the caprolactam sulfuric acid according to following
The step of ester: in the presence of oleum, cyclohexanone oxime is subjected to Beckmann rearrangement.
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| DE1545617A1 (en) * | 1951-01-28 | 1969-08-07 | Basf Ag | Process for the rearrangement of cyclohexanone oxime into epsilon-caprolactam by the action of polyphosphoric acid |
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| CN101168525A (en) * | 2007-11-01 | 2008-04-30 | 湘潭大学 | Method for preparing caprolactam |
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