CN106397478A - Production process of low-chloride amido-trimethylene phosphonic acid (ATMP) - Google Patents
Production process of low-chloride amido-trimethylene phosphonic acid (ATMP) Download PDFInfo
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- CN106397478A CN106397478A CN201610784492.7A CN201610784492A CN106397478A CN 106397478 A CN106397478 A CN 106397478A CN 201610784492 A CN201610784492 A CN 201610784492A CN 106397478 A CN106397478 A CN 106397478A
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 30
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 42
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 30
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims abstract description 20
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims abstract description 14
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 14
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 13
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims abstract description 6
- 230000002411 adverse Effects 0.000 claims description 36
- 230000001174 ascending effect Effects 0.000 claims description 36
- 238000003756 stirring Methods 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 238000005516 engineering process Methods 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 238000007599 discharging Methods 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 238000004140 cleaning Methods 0.000 claims description 9
- 235000013305 food Nutrition 0.000 claims description 9
- 238000004886 process control Methods 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 16
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 abstract description 8
- 235000019270 ammonium chloride Nutrition 0.000 abstract description 4
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 description 25
- 238000000034 method Methods 0.000 description 9
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- HTJDQJBWANPRPF-UHFFFAOYSA-N Cyclopropylamine Chemical group NC1CC1 HTJDQJBWANPRPF-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- YACKEPLHDIMKIO-UHFFFAOYSA-N methylphosphonic acid Chemical compound CP(O)(O)=O YACKEPLHDIMKIO-UHFFFAOYSA-N 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
- C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
Abstract
The invention discloses a production process of low-chloride amido-trimethylene phosphonic acid (ATMP). According to the production process, phosphorous acid, formaldehyde, hydrochloric acid and ammonium bicarbonate are taken as raw materials so as to prepare ATMP through the following steps. The invention provides a brand-new production process of ATMP. According to a traditional process for preparing ATMP, ammonium chloride, formaldehyde and phosphorous acid are generally used as raw materials; due to intrinsic properties of the raw materials, the chloride ion content of the prepared product is generally about 1%. However, according to the production process provided by the invention, raw materials are replaced, the chloride ion content of prepared ATMP is about 0.1% and is greatly lowered, and the application prospect of ATMP is also expanded.
Description
Technical field
The present invention relates to a kind of production technology of ATMP is and in particular to a kind of low chloro amido trimethylene
The production technology of phosphonic acids.
Background technology
ATMP (ATMP) is a kind of water treatment agent, has good chelating, lower bound suppression and lattice
Distortion acts on.Scaling salt class in water can be stoped to form incrustation scale, the particularly formation of calcium carbonate scale.Stable chemical nature in water,
Not facile hydrolysiss.When concentration is higher in water, there is good corrosion mitigating effect.ATMP is cold for the circulation of thermal power plant, oil plant
But water, oil field reinjection water system.The effect reducing hardware or corrosion of piping and fouling can be played.In the row such as textile printing and dyeing
Industry is used as metal ion chelation agent it can also be used to metal conditioner etc..Its chemical stability is good, not facile hydrolysiss, and resistance to height
Temperature, during with compounding uses such as zinc salt, copolymers, has good cooperative effect and threshold effect.Also have good at high doses
Good corrosion inhibition, and belong to nontoxic, non-pollution culture, there is good dispersing and antisludging performance to calcium carbonate scale.
Through patent retrieval, the technical scheme being directed to ATMP (ATMP) is open, such as China Patent No.
ZL 201310218801.0, invention and created name is：A kind of low three methene ATMPs and preparation method thereof, should
Application case is related to a kind of ATMP preparation method of low effective content；China Patent No. ZL 201110116738.0,
Authorized announcement date is on November 07th, 2012, and invention and created name is：A kind of production technology of ATMP, this application
Case is related to a kind of ATMP preparation method；ATMP synthesis material involved by two patents is chlorine
Change ammonium, formaldehyde and phosphorous acid, process route is essentially all to put in reactor by ammonium chloride and phosphorous acid aqueous solution, after intensification
Deca formalin, insulation reaction for a period of time, concentrates, and the regulation content that adds water obtains product.This process adopts a step
Synthetic method, with short production cycle, raw material is easy to get, low production cost, and repeatability is preferably it is easy to industrialized production, but chlorine in product
Ion concentration is between 10000～40000ppm.Chloride ion has high polarity to promote corrosion reaction, has very strong penetrating again
Property, penetrate readily through the protecting film of metal surface, gap corrosion and pitting, therefore, limit it in water process, iron and steel, mixed
The application of the industries such as solidifying soil, the preparation technology therefore developing low chloro amido trimethylene phosphonic becomes research emphasis.
Content of the invention
Present invention aims to the deficiencies in the prior art, now provide one kind to solve existing process and prepare amino three
The higher problem of chloride ion in methene phosphoric acid product, develops the production work of environment amenable low chloro amido trimethylene phosphonic
Skill.
For solving above-mentioned technical problem, the technical solution used in the present invention is：A kind of low chloro amido trimethylene phosphonic
Production technology, its innovative point is：With phosphorous acid, formaldehyde, hydrochloric acid and ammonium hydrogen carbonate as raw material, complete low chlorine according to following steps
The production technology of ATMP；Described comprise the following steps that：
(1) cleaning reactor and relevant device, closes reactor bottom valve；
(2) by 2000～3800 weight portion 80% liquid phosphorous acid suction reactor；
(3) open solid dog-house, add 400～1500 weight portion food grade ammonium bicarbonate, add and finish, open condensation
Device, stirring, heat temperature raising；
(4) when temperature is raised to 0～90 DEG C, Deca hydrochloric acid 80～900 weight portion, micro- negative in Deca process control reactor
Pressure condition is -0.01～0mpa, time for adding 1～5 hour；
(5) after completion of dropwise addition, continue to be warmed up to 50～130 DEG C, start Deca formalin 1800～4500 weight portion, control
In kettle during Deca processed, between 55～135 DEG C, time for adding controlled at 2～8 hours feed temperature；
(6), after formalin completion of dropwise addition, it is incubated 1～5 hour at 60～130 DEG C；
(7) continue concentration of heating, until feed liquid is concentrated to thick, concentration time controlled at 2～20 hours；
(8), after concentration terminates, stop stirring, unlatching reactor bottom steam rushes steam valve door and carries out qi of chong channel ascending adversely, during qi of chong channel ascending adversely,
Deca deionized water 200～1200 weight portion in six times, during qi of chong channel ascending adversely, controls 80～150 DEG C of temperature；
(9) after qi of chong channel ascending adversely terminates, open stirring, add deionized water to adjust content into reactor, drop to 20 when temperature～
When 100 DEG C, add proper amount of active carbon stirring decolouring 1 hour, open reactor bottom discharge valve discharging, and discharging was carried out
Filter；
Reaction equation is as follows：
Beneficial effects of the present invention are as follows：The invention provides a kind of production work of brand-new ATMP
Skill, it is ammonium chloride, formaldehyde and phosphorous acid that traditional handicraft prepare ATMP to generally use raw material, due to raw material itself
Characteristic, the product chloride ion content prepared is typically 1% about, and uses this technique to change raw material, the ATMP chlorine prepared
Ion 0.1% about, greatly reduces the content of chloride ion, also extends the application prospect of ATMP.
Brief description
Fig. 1 is the process chart of the present invention.
Specific embodiment
Hereinafter embodiments of the present invention are illustrated by particular specific embodiment, those skilled in the art can be by this explanation
Content disclosed by book understands other advantages and effect of the present invention easily.
It is illustrated in figure 1 the process chart of the present invention；
Reaction equation is as follows：
Embodiment 1
A kind of production technology of low chloro amido trimethylene phosphonic, concretely comprises the following steps：Cleaning reactor and relevant device, close
Close reactor bottom valve；By 2200 kilogram of 80% liquid phosphorous acid suction reactor.Open solid dog-house, add 600 kilograms of foods
Grade ammonium hydrogen carbonate, adds and finishes, and opens condenser, stirring, heat temperature raising.When temperature is raised to 40 DEG C, Deca hydrochloric acid 600 is public
Jin, in Deca process control reactor, micro-vacuum state is -0.02～-0.01mpa, time for adding 4 hours；After completion of dropwise addition,
Continue to be warmed up to 80 DEG C, start 3500 kilograms of Deca formalin, in kettle during control Deca, feed temperature is at 85～95 DEG C
Between, time for adding controlled at 4 hours；After completion of dropwise addition, it is incubated 2 hours at 95～100 DEG C, continues concentration of heating, until material
Liquid is concentrated to thick, and concentration time controlled at 10 hours；After concentration terminates, stop stirring, open the punching of reactor bottom steam
Steam valve door carries out qi of chong channel ascending adversely, during qi of chong channel ascending adversely, 800 kilograms of Deca deionized water in six times, during qi of chong channel ascending adversely, control temperature 100～
110℃；After qi of chong channel ascending adversely terminates, open stirring, add deionized water to adjust content into reactor, when temperature drops to about 50 DEG C,
Add 30 kilograms of activated carbon stirring decolourings 1 hour, open reactor bottom discharge valve discharging, and discharging is filtered.Warp
Detection, ATMP content 51.4%, chloride ion content 920ppm.
Embodiment 2
A kind of production technology of low chloro amido trimethylene phosphonic, concretely comprises the following steps：Cleaning reactor and relevant device, close
Close reactor bottom valve；By 2500 kilogram of 80% liquid phosphorous acid suction reactor.Open solid dog-house, add 700 kilograms of foods
Grade ammonium hydrogen carbonate, adds and finishes, and opens condenser, stirring, heat temperature raising.When temperature is raised to 50 DEG C, Deca hydrochloric acid 500 is public
Jin, in Deca process control reactor, micro-vacuum state is -0.02～-0.01mpa, time for adding 4.5 hours；Completion of dropwise addition
Afterwards, continue to be warmed up to 90 DEG C, start 3200 kilograms of Deca formalin, control during Deca in kettle feed temperature 95～
Between 105 DEG C, time for adding controlled at 4 hours；After completion of dropwise addition, it is incubated 2 hours at 100～110 DEG C, continues concentration of heating,
Until feed liquid is concentrated to thick, concentration time controlled at 12 hours；After concentration terminates, stop stirring, open reactor bottom
Steam rushes steam valve door and carries out qi of chong channel ascending adversely, during qi of chong channel ascending adversely, 600 kilograms of Deca deionized water in six times, and during qi of chong channel ascending adversely, control temperature
100～110 DEG C；After qi of chong channel ascending adversely terminates, open stirring, add deionized water to adjust content, when temperature drops to 50 DEG C into reactor
When, add proper amount of active carbon stirring decolouring 1 hour, open reactor bottom discharge valve discharging, and discharging is filtered.Warp
Detection, ATMP content 51.7%, chloride ion content 810ppm.
Embodiment 3
A kind of production technology of low chloro amido trimethylene phosphonic, concretely comprises the following steps：Cleaning reactor and relevant device, close
Close reactor bottom valve；By 3000 kilogram of 80% liquid phosphorous acid suction reactor.Open solid dog-house, add 800 kilograms of foods
Grade ammonium hydrogen carbonate, adds and finishes, and opens condenser, stirring, heat temperature raising.When temperature is raised to 50 DEG C, Deca hydrochloric acid 400 is public
Jin, in Deca process control reactor, micro-vacuum state is -0.02～-0.01mpa, time for adding 4.5 hours；Completion of dropwise addition
Afterwards, continue to be warmed up to 100 DEG C, start 3000 kilograms of Deca formalin, control during Deca in kettle feed temperature 95～
Between 105 DEG C, time for adding controlled at 4 hours；After completion of dropwise addition, it is incubated 2 hours at 100～110 DEG C, continues concentration of heating,
Until feed liquid is concentrated to thick, concentration time controlled at 15 hours；After concentration terminates, stop stirring, open reactor bottom
Steam rushes steam valve door and carries out qi of chong channel ascending adversely, during qi of chong channel ascending adversely, 600 kilograms of Deca deionized water in six times, and during qi of chong channel ascending adversely, control temperature
110～120 DEG C；After qi of chong channel ascending adversely terminates, open stirring, add deionized water to adjust content, when temperature drops to 90 DEG C into reactor
When, add proper amount of active carbon stirring decolouring 1 hour, open reactor bottom discharge valve discharging, and discharging is filtered.Warp
Detection, ATMP content 52.4%, chloride ion content 790ppm.
Embodiment 4
A kind of production technology of low chloro amido trimethylene phosphonic, concretely comprises the following steps：Cleaning reactor and relevant device, close
Close reactor bottom valve；By 3000 kilogram of 80% liquid phosphorous acid suction reactor.Open solid dog-house, add 750 kilograms of foods
Grade ammonium hydrogen carbonate, adds and finishes, and opens condenser, stirring, heat temperature raising.When temperature is raised to 50 DEG C, Deca hydrochloric acid 400 is public
Jin, in Deca process control reactor, micro-vacuum state is -0.02～-0.01mpa, time for adding 4.5 hours；Completion of dropwise addition
Afterwards, continue to be warmed up to 100 DEG C, start 3000 kilograms of Deca formalin, control during Deca in kettle feed temperature 95～
Between 105 DEG C, time for adding controlled at 4 hours；After completion of dropwise addition, it is incubated 2 hours at 100～110 DEG C, continues concentration of heating,
Until feed liquid is concentrated to thick, concentration time controlled at 12 hours；After concentration terminates, stop stirring, open reactor bottom
Steam rushes steam valve door and carries out qi of chong channel ascending adversely, during qi of chong channel ascending adversely, Deca deionized water 400 weight portion in six times, and during qi of chong channel ascending adversely, control temperature
110～120 DEG C of degree；After qi of chong channel ascending adversely terminates, open stirring, add deionized water to adjust content, when temperature drops to 80 into reactor
DEG C when, add proper amount of active carbon stirring decolouring 1 hour, open reactor bottom discharge valve discharging, and discharging is filtered.
After testing, ATMP content 51.8%, chloride ion content 680ppm.
Embodiment 5
A kind of production technology of low chloro amido trimethylene phosphonic, is former with phosphorous acid, formaldehyde, hydrochloric acid and ammonium hydrogen carbonate
Material, completes the production technology of low chloro amido trimethylene phosphonic according to following steps；Comprise the following steps that：Cleaning reactor and phase
Pass equipment, closes reactor bottom valve；By 2000 weight portion 80% liquid phosphorous acid suction reactor；Open solid dog-house, plus
Enter 400 weight portion food grade ammonium bicarbonate, add and finish, open condenser, stirring, heat temperature raising；When temperature is raised to 0 DEG C,
Deca hydrochloric acid 80 weight portion, in Deca process control reactor, micro-vacuum state is -0.02mpa, time for adding 1 hour；Deca
After end, continue to be warmed up to 50 DEG C, start Deca formalin 1800 weight portion, in kettle during control Deca, feed temperature exists
Between 55 DEG C, time for adding controlled at 2 hours；After formalin completion of dropwise addition, it is incubated 1 hour at 60 DEG C；Continue concentration of heating,
Until feed liquid is concentrated to thick, concentration time controlled at 2 hours；After concentration terminates, stop stirring, open reactor bottom and steam
Vapour rushes steam valve door and carries out qi of chong channel ascending adversely, during qi of chong channel ascending adversely, Deca deionized water 200 weight portion in six times, and during qi of chong channel ascending adversely, control temperature
80℃；After qi of chong channel ascending adversely terminates, open stirring, add deionized water to adjust content into reactor, when temperature drops to 20 DEG C, add
Proper amount of active carbon stirring decolouring 1 hour, opens reactor bottom discharge valve discharging, and discharging is filtered.After testing,
ATMP content 52.1%, chloride ion content 690ppm.
Embodiment 6
A kind of production technology of low chloro amido trimethylene phosphonic, is former with phosphorous acid, formaldehyde, hydrochloric acid and ammonium hydrogen carbonate
Material, completes the production technology of low chloro amido trimethylene phosphonic according to following steps；Comprise the following steps that：Cleaning reactor and phase
Pass equipment, closes reactor bottom valve；By 3800 weight portion 80% liquid phosphorous acid suction reactor；Open solid dog-house, plus
Enter 1500 weight portion food grade ammonium bicarbonate, add and finish, open condenser, stirring, heat temperature raising；When temperature is raised to 90 DEG C
When, Deca hydrochloric acid 900 weight portion, in Deca process control reactor, micro-vacuum state is -0.01mpa, time for adding 5 hours；
After completion of dropwise addition, continue to be warmed up to 130 DEG C, start Deca formalin 4500 weight portion, feed liquid in kettle during control Deca
Between 135 DEG C, time for adding controlled at 8 hours temperature；After formalin completion of dropwise addition, it is incubated 5 hours at 130 DEG C；Continue
Heat concentration, until feed liquid is concentrated to thick, concentration time controlled at 20 hours；After concentration terminates, stop stirring, open anti-
Answer kettle bottom steam to rush steam valve door and carry out qi of chong channel ascending adversely, during qi of chong channel ascending adversely, Deca deionized water 1200 weight portion in six times, qi of chong channel ascending adversely process
In, control 150 DEG C of temperature；After qi of chong channel ascending adversely terminates, open stirring, add deionized water to adjust content into reactor, when temperature fall
During to 100 DEG C, add proper amount of active carbon stirring decolouring 1 hour, open reactor bottom discharge valve discharging, and discharging is carried out
Filter.After testing, ATMP content 51.8%, chloride ion content 680ppm.
Embodiment 7
A kind of production technology of low chloro amido trimethylene phosphonic, is former with phosphorous acid, formaldehyde, hydrochloric acid and ammonium hydrogen carbonate
Material, completes the production technology of low chloro amido trimethylene phosphonic according to following steps；Comprise the following steps that：Cleaning reactor and phase
Pass equipment, closes reactor bottom valve；By 2900 weight portion 80% liquid phosphorous acid suction reactor；Open solid dog-house, plus
Enter 950 weight portion food grade ammonium bicarbonate, add and finish, open condenser, stirring, heat temperature raising；When temperature is raised to 45 DEG C,
Deca hydrochloric acid 490 weight portion, in Deca process control reactor, micro-vacuum state is -0.015mpa, time for adding 3 hours；Drip
Plus after terminating, continue to be warmed up to 90 DEG C, start Deca formalin 3200 weight portion, feed temperature in kettle during control Deca
Between 95 DEG C, time for adding controlled at 5 hours；After formalin completion of dropwise addition, it is incubated 3 hours at 95 DEG C；Continue to heat dense
Contracting, until feed liquid is concentrated to thick, concentration time controlled at 11 hours；After concentration terminates, stop stirring, open reactor bottom
Portion's steam rushes steam valve door and carries out qi of chong channel ascending adversely, during qi of chong channel ascending adversely, Deca deionized water 700 weight portion in six times, and during qi of chong channel ascending adversely, control
120 DEG C of temperature；After qi of chong channel ascending adversely terminates, open stirring, add deionized water to adjust content, when temperature drops to 60 DEG C into reactor
When, add proper amount of active carbon stirring decolouring 1 hour, open reactor bottom discharge valve discharging, and discharging is filtered.Warp
Detection, ATMP content 51.8%, chloride ion content 680ppm.
The invention provides a kind of production technology of brand-new ATMP, traditional handicraft prepares amino trimethylene
It is ammonium chloride, formaldehyde and phosphorous acid that methylphosphonic acid generally uses raw material, due to raw material self character, the product chloride ion prepared
Content is typically 1% about, and uses this technique to change raw material, and the ATMP chloride ion prepared 0.1% about, greatly reduces
The content of chloride ion, also extends the application prospect of ATMP.
Above-described embodiment is presently preferred embodiments of the present invention, is not the restriction to technical solution of the present invention, as long as
The technical scheme that can realize on the basis of above-described embodiment without creative work, is regarded as falling into patent of the present invention
Rights protection scope in.
Claims (1)
1. a kind of production technology of low chloro amido trimethylene phosphonic it is characterised in that：With phosphorous acid, formaldehyde, hydrochloric acid and carbonic acid
Hydrogen ammonium is raw material, completes the production technology of low chloro amido trimethylene phosphonic according to following steps；Described comprise the following steps that：
(1) cleaning reactor and relevant device, closes reactor bottom valve；
(2) by 2000～3800 weight portion 80% liquid phosphorous acid suction reactor；
(3) open solid dog-house, add 400～1500 weight portion food grade ammonium bicarbonate, add and finish, open condenser,
Stirring, heat temperature raising；
(4) when temperature is raised to 0～90 DEG C, Deca hydrochloric acid 80～900 weight portion, tiny structure shape in Deca process control reactor
State is -0.01～0mpa, time for adding 1～5 hour；
(5) after completion of dropwise addition, continue to be warmed up to 50～130 DEG C, start Deca formalin 1800～4500 weight portion, control and drip
Plus during in kettle feed temperature between 55～135 DEG C, time for adding controlled at 2～8 hours；
(6), after formalin completion of dropwise addition, it is incubated 1～5 hour at 60～130 DEG C；
(7) continue concentration of heating, until feed liquid is concentrated to thick, concentration time controlled at 2～20 hours；
(8), after concentration terminates, stop stirring, unlatching reactor bottom steam rushes steam valve door and carries out qi of chong channel ascending adversely, during qi of chong channel ascending adversely, divide six
The deionized water of secondary Deca 200～1200 weight portion, during qi of chong channel ascending adversely, controls 80～150 DEG C of temperature；
(9) after qi of chong channel ascending adversely terminates, open stirring, add deionized water to adjust content, when temperature drops to 20～100 DEG C into reactor
When, add certain carbon content active stirring decolouring 1 hour, open reactor bottom discharge valve discharging, and discharging is filtered；
Reaction equation is as follows：
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