CN105819467B - A kind of integrated conduct method of titanate esters byproduct ammonium chloride - Google Patents
A kind of integrated conduct method of titanate esters byproduct ammonium chloride Download PDFInfo
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- CN105819467B CN105819467B CN201610313680.1A CN201610313680A CN105819467B CN 105819467 B CN105819467 B CN 105819467B CN 201610313680 A CN201610313680 A CN 201610313680A CN 105819467 B CN105819467 B CN 105819467B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/16—Halides of ammonium
- C01C1/164—Ammonium chloride
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Abstract
The present invention relates to a kind of integrated conduct method of titanate esters byproduct ammonium chloride, comprise the following steps：Byproduct ammonium chloride is added water and breaks into ammonium chloride slurry, wherein byproduct ammonium chloride accounts for the 28 50% of ammonium chloride slurry gross weight；Slurry is subjected to heating distillation, distillation, which is separated, obtains ammonium chloride slurry after oil water mixture；The oil water mixture separates oil phase and aqueous phase by stratification；By ammonium chloride slurry decrease temperature crystalline, product ammonium chloride is then obtained by centrifugation；Centrifuge obtained mother liquor return to step（1）Repeat to apply mechanically as mashing water.The present invention relates to integrated conduct method but can be well solve fall oven drying method shortcoming, quality after the processing of byproduct ammonium chloride is significantly improved, and production tail gas and the dangerous solid waste of production can be comprehensively utilized, company is realized without all three waste discharges, it is truly realized clean manufacturing, it can also realize that solvent, alcohol are recycled simultaneously, reduce cost.
Description
Technical field
The present invention relates to titanate esters production technology field, at specifically a kind of novel integrated of titanate esters byproduct ammonium chloride
Reason method.
Background technology
In the production of titanate esters, generally reacted at present using corresponding alcohol and titanium tetrachloride in suitable solvent, than
If tetra-n-butyl titanate is butanol with titanium tetrachloride in heptane（It is used as solvent）Middle reaction is obtained, and tetraisopropyl titanate is isopropanol
React and obtain in heptane with titanium tetrachloride；In order to promote reaction forward to carry out, the chlorination typically generated with ammonia neutralization reaction
Hydrogen, final arrives product titanate esters and byproduct ammonium chloride；Byproduct ammonium chloride after centrifuge rejection filter by obtaining, but centrifugation
Still containing excessive alcohol in substantial amounts of solvent and reaction in ammonium chloride afterwards, wherein in byproduct ammonium chloride, ammonium chloride content is about
For 90 ~ 92%, solvent is about 6 ~ 8%, and alcohol content is about 1.5 ~ 2.0,；Above-mentioned ammonium chloride obviously can not as fertilizer or its
He uses purposes, while because the presence of solvent and alcohol causes the inflammable risk of product very high, traditional way is after being dried
Recycling design and alcohol, ammonium chloride are sold as byproduct, and oven drying method processing is very inconvenient in actual operation, is primarily due to：
1st, oven drying method yield is very low, the performance of serious restriction production capacity；2nd, the organic matter group of the dried chlorination ammonium product of existing oven drying method
Divide 0.5% or so, and material outward appearance is fine-powdered, product granularity very little, particle diameter is less than 0.5mm, it might even be possible to flow；Material
Density is low, and bulk density has very inconvenient far below finished product ammonium chloride on the market when client is used；3rd, oven drying method can only be located
Manage ammonium chloride, produce the discarded object that other links produce need it is respective handled, environmentally friendly operating pressure is big and cost is high.Dry
The disadvantages mentioned above of dry method causes part company not deal with directly to sell at a low price, and very big hidden danger is caused to environment, safety.
In addition, titanate esters have production tail gas in normally producing, tail gas is mainly reactor charging process, reaction latter end mistake
The ammonia of amount can also carry a small amount of solvent secretly and alcohol is evaporated；Also contain partial organic substances in the exhaust of rotary process；Refined
The ammonia being dissolved in journey in material can be evaporated, and the on-condensible gas in system can also carry a large amount of solvents and alcohol secretly, and tail gas is usual
Handled by the way of water absorbs, it is ammonia, solvent and alcohol that can produce the main component in substantial amounts of production waste water, water.
Directly discharge can be polluted to environment.In addition, alcohol is generated after sour titanate esters with titanium tetrachloride reaction, distilation need to be carried out,
The original processing mode of titanate esters bottoms after distillation, later by improving, will distill as hazardous waste disposal
Residue is put into hydrolysis kettle, and the hydrolysis that adds water is carried out under 60 degrees celsius, the aqueous solution of titanium dioxide and alcohol, the method is obtained
The problem of with solid waste hazardous waste can be solved, but can really derive high alcohol-content waste water, it still can not realize clean manufacturing.
The content of the invention
For the drawbacks described above of prior art, the present invention provides a kind of novel integrated processing of titanate esters byproduct ammonium chloride
Method, its primary and foremost purpose be solve oven drying method processing chloride yield it is low, it is off quality the problem of, realize the recovery of ammonium chloride
Recycle, next to that realizing production tail gas and the dangerous solid waste comprehensive utilization of production, realize clean manufacturing.
Technical scheme comprises the following steps：
（1）Byproduct ammonium chloride is added water and breaks into ammonium chloride slurry, wherein byproduct ammonium chloride accounts for ammonium chloride slurry gross weight
The 28-50% of amount；
（2）Slurry is subjected to heating distillation, distillation, which is separated, obtains ammonium chloride slurry after oil water mixture；The oil mixing with water
Thing separates oil phase and aqueous phase by stratification；
Oil phase is obtained into solvent by distillation and/or distillation operation purification, solvent is returned in titanate esters production technology and repeated
Use, the raffinate of distillation and rectifying is back to step（1）Repetition is applied mechanically；
Aqueous phase is obtained into alcohol by distillation and/or distillation operation purification, alcohol is returned in titanate esters preparation technology and reused,
Distillation and distillation residual liquid are back to step（1）Repetition is applied mechanically；
（3）By ammonium chloride slurry decrease temperature crystalline, product ammonium chloride is then obtained by centrifugation；Obtained mother liquor is centrifuged to return
Step（1）Repeat to apply mechanically as mashing water.
It is preferred that, the step（1）The control of ammonium chloride mass concentration is 40% in slurry.
It is preferred that, the step（2）Middle slurry vapo(u)rizing temperature control is at 80-110 degrees Celsius.
It is preferred that, titanate esters tail gas absorption water is added into hydrochloric acid and neutralized, step is then back to（1）Repeated as mashing with water
Apply mechanically.
It is preferred that, titanate esters bottoms are added water hydrolysis, filter cake and centrifuge mother liquor are obtained after centrifugation, after filter cake is scrubbed
Obtain product titanium dioxide, wash water and centrifuge mother liquor return to step（1）Repeat to apply mechanically as mashing water.
It is preferred that, the step（2）Oil phase initially enters crude steam kettle, then leads to steam and distills at 80 degrees celsius,
First infinite reflux 30 minutes, then gradually adjusts reflux ratio to 1:10, solvent is distilled；Distill obtained solvent further defeated
It is sent to rectifying still rectifying；Distillation operation mode is identical with distillating method in crude steam kettle, and the solvent after rectifying returns to titanate esters life
Applied mechanically in production. art, step is returned to after the vinasse cooling of thick steaming and rectifying（1）Middle recycled.
It is preferred that, the step（2）Aqueous phase initially enters crude steam kettle, then leads to steam and is carried out between 80 ~ 90 degrees Celsius
Distillation, regulation reflux ratio to 1:3, alcohol is distilled；Then alcohol distillation obtained is transported to rectifying still and carries out rectifying, control
Rectification temperature is 82 degrees Celsius, and reflux ratio is controlled 1:3, the alcohol that rectifying is obtained is returned to be applied mechanically in titanate esters production technology, essence
Evaporate raffinate and return to crude steam kettle redistillation, crude steam kettle vinasse returns to step（1）Middle recycled.
It is preferred that, the temperature control of the ammonium chloride slurry decrease temperature crystalline is 40 degrees Celsius.
The step（2）Zeolite is added when middle oil phase distillation and/or distillation operation, described zeolite refers to ZSM-5 molecules
Sieve or modified red stilbite, modified red stilbite method of modifying is：By the epidesmine between 80~100 mesh with 10%
Digestion 12h at 80 DEG C of NH4Cl solution, is soaked 3 days with 2mol/L HCl solution, is washed to no Cl-, and 120 DEG C dry, according still further to
Solid-liquid weight compares 1：5 dry at concentrated phosphoric acid is soaked 7 days, 100 DEG C, move to porcelain crucible in microwave stove heat 10min, take out cooling
After be washed with water, then 120 DEG C drying, obtain modified zeolite.
The step（2）Zeolite is added when middle aqueous phase distillation and/or distillation operation, described zeolite refers to ZSM-5 molecules
Sieve or modified red stilbite, modified red stilbite method of modifying is：By the epidesmine between 80~100 mesh with 10%
NH4Digestion 12h at 80 DEG C of Cl solution, is soaked 3 days with 2mol/L HCl solution, is washed to no Cl-, 120 DEG C of drying, according still further to solid
Liquid weight compares 1：5 dry at concentrated phosphoric acid is soaked 7 days, 100 DEG C, move to porcelain crucible in microwave stove heat 10min, take out after cooling
It is washed with water, then in 120 DEG C of drying, obtains modified zeolite.
The present invention relates to integrated conduct method but can be well the shortcoming for solving oven drying method, at byproduct ammonium chloride
Quality after reason is significantly improved；The ammonium chloride content that the present invention is obtained is more than 99.9%, and does not detect organic constituentses, crystal
Grain is big, and particle diameter is in more than 3mm, and bulk density is big, and same packaging bag is high compared with the packed weight for the ammonium chloride that oven drying method is obtained by 25%
More than, GB/T2946-2008 requirement can be reached；And production tail gas and the dangerous solid waste of production can be comprehensively utilized, realized
Company is truly realized clean manufacturing without all three waste discharges, while can also realize that solvent, alcohol are recycled, reduces into
This.
Embodiment
Below by taking the byproduct ammonium chloride of tetra-n-butyl titanate as an example, next the present invention is described further.Metatitanic acid four
The byproduct ammonium chloride processing mode of isopropyl ester is identical, and difference is the temperature when alcohol in separating alcohol-water mixture
Control is slightly different.
Embodiment 1
A kind of novel integrated processing method of titanate esters byproduct ammonium chloride, comprises the following steps：
（1）Expect under the byproduct ammonium chloride that is obtained by centrifuge rejection filter is direct in mashing kettle, be previously added in kettle from
Water, is beaten 30 minutes under stirring, and now ammonium chloride and circulating mother liquor are broken into slurry, and byproduct ammonium chloride accounts for chlorination
The 40% of ammonium slurry gross weight.
（2）The slurry accomplished fluently is put into distillation still, is led to steam and is carried out air-distillation, material begins with material at 80 degrees Celsius
Steam, the material steamed includes heptane（Solvent）, n-butanol, water, early stage solvent is relatively more, as solvent is gradually distilled
Out, temperature of charge is gradually increasing in kettle, to 110 degrees Celsius, and solvent, alcohol in kettle in material can be distilled all.
（3）Distill the ammonium chloride slurry finished and be transferred to decrease temperature crystalline in crystallization kettle, cool to 40 degrees Celsius and start crystallization；
The tiny grain crystalline of ammonium chloride in crystallization process, grow up, obtain the byproduct chlorine with equigranular and specification with commercially available ammonium chloride
Change ammonium.The slurry of advantages of good crystallization is dried by centrifuge, you can obtain the product ammonium chloride of water content about 5%, centrifuges obtained mother liquor
Then enter mother liquor holding tank, then recycled again by being pumped into mashing kettle.Solvent, alcohol, the mixture of water distilled
First pass around standing, layering, solvent layer separated with water layer, solvent accounts for steaming the 30% of material total amount, other parts for alcohol and
The mixture of water.Isolated thick solvent and alcohol, aqueous mixtures, thick solvent and alcohol, aqueous mixtures are respectively delivered to crude steam kettle and entered
Row distillation, purification.
（4）, thick Solvents Solvent enter crude steam kettle after, lead to steam, distillation, distilled at 80 degrees celsius, first entirely
Backflow.After backflow 30 minutes, backflow ratio, final regulation reflux ratio 1 are gradually adjusted:10, solvent is distilled, distillation is obtained
Solvent be further conveyed to rectifying still rectifying.Distillation operation mode is identical with thick solvent distillating method, and the solvent after rectifying can
Applied mechanically with returning in titanate esters production, recycled, solvent in mashing kettle are returned to after the vinasse cooling of thick steaming and rectifying
No waste mine is produced in still-process.
（5）, alcohol, aqueous mixtures enter crude steam kettle after, lead to steam, distilled between 80 ~ 90 degrees Celsius, regulation flow back
Than 1:3, the concentration of alcohol is improved, by purification, the solution of alkoxide component about 83% is obtained, rectifying still is then transported to again and carries out essence
Evaporate, control 82 degrees Celsius of temperature, reflux ratio 1:3, the alcohol of high-purity is obtained, alcohol returns to titanate esters workshop and used, and distillation residual liquid is returned
Crude steam kettle distillation is returned to, crude steam kettle vinasse returns to recycled in mashing kettle.
Embodiment 2
A kind of novel integrated processing method of titanate esters byproduct ammonium chloride, the difference with embodiment 1 is, step（1）
Middle byproduct ammonium chloride accounts for the 28% of ammonium chloride slurry gross weight.
Embodiment 3
A kind of novel integrated processing method of titanate esters byproduct ammonium chloride, the difference with embodiment 1 is, step（1）
Middle byproduct ammonium chloride accounts for the 50% of ammonium chloride slurry gross weight.
Embodiment 4
A kind of novel integrated processing method of titanate esters byproduct ammonium chloride, the difference with embodiment 1 is, by step
（1）Middle running water replaces with crystalline mother solution, the step that step (3) is obtained（4）Obtained thick steaming and vinasse, the step of rectifying
（5）The mixture of obtained crude steam kettle vinasse three.
Embodiment 5
A kind of novel integrated processing method of titanate esters byproduct ammonium chloride, the difference with embodiment 1 is, by titanate esters
Tail gas absorption water adds hydrochloric acid and is neutralized to pH after 6-8, to be then back to step（1）Mix and repeated as mashing with water with running water
Apply mechanically.
Embodiment 6
A kind of novel integrated processing method of titanate esters byproduct ammonium chloride, the difference with embodiment 1 is, by titanate esters
Bottoms are added water hydrolysis, and filter cake and centrifuge mother liquor are obtained after centrifugation, obtain product titanium dioxide after filter cake is scrubbed, wash water and
Centrifuge mother liquor return to step（1）Mixed with running water and repeat to apply mechanically as mashing water.
Embodiment 7
A kind of novel integrated processing method of titanate esters byproduct ammonium chloride, the difference with embodiment 4 is, by titanate esters
Tail gas absorption water adds hydrochloric acid and is neutralized to pH after 6-8, to be then back to step（1）The crystalline mother solution that is obtained with step (3), step
（4）Obtained thick steaming and vinasse, the step of rectifying（5）Obtained crude steam kettle vinasse mixing is repeated as mashing with water
Apply mechanically.
Embodiment 8
A kind of novel integrated processing method of titanate esters byproduct ammonium chloride, the difference with embodiment 4 is, by titanate esters
Bottoms are added water hydrolysis, and filter cake and centrifuge mother liquor are obtained after centrifugation, obtain product titanium dioxide after filter cake is scrubbed, wash water and
Centrifuge mother liquor return to step（1）The crystalline mother solution that is obtained with step (3), step（4）Obtained thick steaming and the vinasse of rectifying,
Step（5）Obtained crude steam kettle vinasse mixing repeats to apply mechanically as mashing water.
Embodiment 9
A kind of novel integrated processing method of titanate esters byproduct ammonium chloride, the difference with embodiment 7 is, by titanate esters
Bottoms are added water hydrolysis, and filter cake and centrifuge mother liquor are obtained after centrifugation, obtain product titanium dioxide after filter cake is scrubbed, wash water and
Centrifuge mother liquor return to step（1）The crystalline mother solution that is obtained with step (3), step（4）Obtained thick steaming and the vinasse of rectifying,
Step（5）The mixing of titanate esters tail gas absorption water repeats to cover as mashing water after obtained crude steam kettle vinasse and neutralization
With.
Embodiment 10
Difference with embodiment 1 is, step（4）In the distillation of thick solvent and during distillation operation, add described boiling
Stone refers to modified red stilbite, and method of modifying is：By the epidesmine between 80~100 mesh with 10% NH4At 80 DEG C of Cl solution
Digestion 12h, is soaked 3 days with 2mol/L HCl solution, is washed to no Cl-, 120 DEG C dry, and compare 1 according still further to solid-liquid weight：5 in
Concentrated phosphoric acid is dried at soaking 7 days, 100 DEG C, is moved to porcelain crucible in microwave stove heat 10min, is washed with water after taking out cooling, then
120 DEG C of drying, obtain modified zeolite.
Embodiment 11
Difference with embodiment 9 is, step（4）In thick solvent distillation and during distillation operation, add described boiling
Stone refers to modified red stilbite, and method of modifying is：By the epidesmine between 80~100 mesh with 10% NH4At 80 DEG C of Cl solution
Digestion 12h, is soaked 3 days with 2mol/L HCl solution, is washed to no Cl-, 120 DEG C dry, and compare 1 according still further to solid-liquid weight：5 in
Concentrated phosphoric acid is dried at soaking 7 days, 100 DEG C, is moved to porcelain crucible in microwave stove heat 10min, is washed with water after taking out cooling, then
120 DEG C of drying, obtain modified zeolite.
Embodiment 12
Difference with embodiment 1 is, step（5）In alcohol, aqueous mixtures distillation and during distillation operation, add described
Zeolite refer to modified red stilbite, method of modifying is：By the epidesmine between 80~100 mesh with 10% NH4Cl solution 80
Digestion 12h at DEG C, is soaked 3 days with 2mol/L HCl solution, is washed to no Cl-, 120 DEG C dry, and compare 1 according still further to solid-liquid weight：
5 dry at concentrated phosphoric acid is soaked 7 days, 100 DEG C, move to porcelain crucible in microwave stove heat 10min, are washed with water after taking out cooling,
Again in 120 DEG C of drying, modified zeolite is obtained.
Embodiment 13
Difference with embodiment 9 is, step（5）In alcohol, aqueous mixtures distillation and during distillation operation, add described
Zeolite refer to modified red stilbite, method of modifying is：By the epidesmine between 80~100 mesh with 10% NH4Cl solution 80
Digestion 12h at DEG C, is soaked 3 days with 2mol/L HCl solution, is washed to no Cl-, 120 DEG C dry, and compare 1 according still further to solid-liquid weight：
5 dry at concentrated phosphoric acid is soaked 7 days, 100 DEG C, move to porcelain crucible in microwave stove heat 10min, are washed with water after taking out cooling,
Again in 120 DEG C of drying, modified zeolite is obtained.
Embodiment 14
Difference with embodiment 11 is, modified red stilbite is replaced with into ZSM-5 molecular sieves.
Embodiment 15
Difference with embodiment 13 is, modified red stilbite is replaced with into ZSM-5 molecular sieves.
Due to forming accessory substance and impurity in titanate esters building-up process, simultaneously because mother liquor and vinasse are applied mechanically,
Product purity is difficult to break through during causing solvent and alcohol distillation or rectification and purification, and the purity of solvent and alcohol is consistently lower than
99%；Specific impurities therein can be adsorbed by adding modified red stilbite or ZSM-5 molecular sieves, product is substantially increased
Purity.Testing simultaneously proves after titanate esters reaction, when distilation, adds modified red stilbite or ZSM-5 molecules
Sieve, also can avoid volatile impurity from being brought into vacuum distillation in finished product, can improve product purity, purer than conventional distil-lation
Degree can improve 2 percentage points.
After process step by the present invention, solvent, alcohol in ammonium chloride are substantially all to be reclaimed, byproduct chlorine
Change ammonium and also obtain good purifying, reach expected purpose, the average purity 99.9% for the ammonium chloride product that embodiment 1-9 is obtained,
Outward appearance, particle diameter and density meet currently marketed product, and particle diameter is in 3-5mm；This method can also be produced to titanate esters simultaneously
In journey good operation is produced in terms of tail gas recycle and production waste processing（Such as use the scheme of embodiment 5-9 technologies）, it is real
The clean manufacturing of existing company：
Tail gas absorption water is neutralized and is transported in crystalline mother solution water pot by one, is used as mashing with water, after then passing through
Continuous distillation, centrifugation, separation, thick steaming, essence steam recycling design and alcohol, and water and vinasse are recycled.Using energy after the method
Enough thorough process for producing waste water, and the valuable article recovery in waste water is used, i.e., fundamentally solve production waste water
Environmental issue, can also reduce production cost, achieve many things at one stroke.
Secondly, bottoms are put into hydrolysis kettle, the hydrolysis that adds water is carried out under 60 degrees celsius, titanium dioxide is obtained
And the aqueous solution of alcohol, then the slurry after hydrolysis is first centrifuged, after filter cake is washed using massive laundering, the alcohol in filter cake rushed
Wash clean, as nontoxic, the harmless product titanium dioxide of filter cake, centrifuge mother liquor enters ammonium chloride processing stream as mashing with water
Journey, is then distilled the alcohol in waste water, solvent etc. by processes such as follow-up centrifugation, distillations, realizes the circulation profit of waste water
With fundamentally realizing clean manufacturing..
It is described above, only it is presently preferred embodiments of the present invention, any those skilled in the art are possibly also with upper
Equivalent technical scheme is changed or be revised as to the technical scheme for stating elaboration to the present invention.Therefore, the skill according to invention
Any simple modification or substitute equivalents that art scheme is carried out, belong to the greatest extent the scope of protection of present invention.
Claims (9)
1. a kind of integrated conduct method of titanate esters byproduct ammonium chloride, it is characterised in that comprise the following steps：
（1）Byproduct ammonium chloride is added water and breaks into ammonium chloride slurry, wherein byproduct ammonium chloride accounts for ammonium chloride slurry gross weight
28-50%；
（2）Slurry is subjected to heating distillation, distillation, which is separated, obtains ammonium chloride slurry after oil water mixture；The oil water mixture leads to
Stratification is crossed, oil phase and aqueous phase is separated；
Oil phase is obtained into solvent by distillation and/or distillation operation purification, solvent is returned in titanate esters production technology and reused,
The raffinate of distillation and rectifying is back to step（1）Repetition is applied mechanically；
Aqueous phase is obtained into alcohol by distillation and/or distillation operation purification, alcohol is returned in titanate esters preparation technology and reused, distillation
And distillation residual liquid is back to step（1）Repetition is applied mechanically；
（3）By ammonium chloride slurry decrease temperature crystalline, product ammonium chloride is then obtained by centrifugation；Centrifuge obtained mother liquor return to step
（1）Repeat to apply mechanically as mashing water；
Titanate esters tail gas absorption water is added into hydrochloric acid to neutralize, step is then back to（1）Repeat to apply mechanically as mashing water.
2. the integrated conduct method of titanate esters byproduct ammonium chloride according to claim 1, it is characterised in that the step
（1）Byproduct ammonium chloride accounts for the 40% of ammonium chloride slurry gross weight in slurry.
3. the integrated conduct method of titanate esters byproduct ammonium chloride according to claim 1, it is characterised in that the step
（2）Middle slurry vapo(u)rizing temperature control is at 80-110 degrees Celsius.
4. the integrated conduct method of titanate esters byproduct ammonium chloride according to claim 1, it is characterised in that by titanate esters
Bottoms are added water hydrolysis, and filter cake and centrifuge mother liquor are obtained after centrifugation, obtain product titanium dioxide after filter cake is scrubbed, wash water and
Centrifuge mother liquor return to step（1）Repeat to apply mechanically as mashing water.
5. the integrated conduct method of titanate esters byproduct ammonium chloride according to claim 1, it is characterised in that the step
（2）Oil phase initially enters crude steam kettle, then leads to steam and distills at 80 degrees celsius, first infinite reflux 30 minutes, then gradually
Reflux ratio is adjusted to 1:10, solvent is distilled；Distill obtained solvent and be further conveyed to rectifying still rectifying；Distillation operation
Mode is identical with distillating method in crude steam kettle, and the solvent after rectifying is returned to be applied mechanically in titanate esters production technology, thick to steam and rectifying
Vinasse cooling after return to step（1）Middle recycled.
6. the integrated conduct method of titanate esters byproduct ammonium chloride according to claim 1, it is characterised in that the step
（2）Aqueous phase initially enters crude steam kettle, then leads to steam and is distilled between 80 ~ 90 degrees Celsius, regulation reflux ratio to 1:3, will
Alcohol is distilled；Then alcohol distillation obtained is transported to rectifying still and carries out rectifying, and it is 82 degrees Celsius to control rectification temperature, backflow
Than controlling 1:3, the alcohol that rectifying is obtained is returned to be applied mechanically in titanate esters production technology, and distillation residual liquid returns to crude steam kettle and steamed again
Evaporate, crude steam kettle vinasse returns to step（1）Middle recycled.
7. the integrated conduct method of titanate esters byproduct ammonium chloride according to claim 1, it is characterised in that the chlorination
The temperature control of ammonium slurry decrease temperature crystalline is 40 degrees Celsius.
8. the integrated conduct method of titanate esters byproduct ammonium chloride according to claim 1, it is characterised in that the step
（2）Zeolite is added when middle oil phase distillation and/or distillation operation, described zeolite refers to ZSM-5 molecular sieves or modified red brightness boiling
Stone, modified red stilbite method of modifying is：By the epidesmine between 80~100 mesh with 10% NH4Digestion at 80 DEG C of Cl solution
12h, is soaked 3 days with 2mol/L HCl solution, is washed to no Cl-, 120 DEG C dry, and compare 1 according still further to solid-liquid weight：5 in dense phosphorus
Acid soak is dried at 7 days, 100 DEG C, is moved to porcelain crucible in microwave stove heat 10min, is washed with water after taking out cooling, then 120
DEG C drying, obtain modified zeolite.
9. the integrated conduct method of titanate esters byproduct ammonium chloride according to claim 1, it is characterised in that the step
（2）Zeolite is added when middle aqueous phase distillation and/or distillation operation, described zeolite refers to ZSM-5 molecular sieves or modified red brightness boiling
Stone, modified red stilbite method of modifying is：By the epidesmine between 80~100 mesh with 10% NH4Digestion at 80 DEG C of Cl solution
12h, is soaked 3 days with 2mol/L HCl solution, is washed to no Cl-, 120 DEG C dry, and compare 1 according still further to solid-liquid weight：5 in dense phosphorus
Acid soak is dried at 7 days, 100 DEG C, is moved to porcelain crucible in microwave stove heat 10min, is washed with water after taking out cooling, then 120
DEG C drying, obtain modified zeolite.
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| CN105503942A (en) * | 2016-01-12 | 2016-04-20 | 江苏苏源辉普化工有限公司 | Continuous production method for triethyl phosphite |
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| CN104892666A (en) * | 2015-06-26 | 2015-09-09 | 四川中萃化工有限公司 | Method for preparing high-purity tributyl phosphate |
| CN105503942A (en) * | 2016-01-12 | 2016-04-20 | 江苏苏源辉普化工有限公司 | Continuous production method for triethyl phosphite |
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