CN102408358A - One-step safety production method of guanidine nitrate - Google Patents
One-step safety production method of guanidine nitrate Download PDFInfo
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- CN102408358A CN102408358A CN201110432650XA CN201110432650A CN102408358A CN 102408358 A CN102408358 A CN 102408358A CN 201110432650X A CN201110432650X A CN 201110432650XA CN 201110432650 A CN201110432650 A CN 201110432650A CN 102408358 A CN102408358 A CN 102408358A
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- NDEMNVPZDAFUKN-UHFFFAOYSA-N guanidine;nitric acid Chemical compound NC(N)=N.O[N+]([O-])=O.O[N+]([O-])=O NDEMNVPZDAFUKN-UHFFFAOYSA-N 0.000 title abstract 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 69
- 238000000034 method Methods 0.000 claims abstract description 55
- 239000004202 carbamide Substances 0.000 claims abstract description 40
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 39
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000002994 raw material Substances 0.000 claims abstract description 25
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 12
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 239000000741 silica gel Substances 0.000 claims abstract description 10
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- MJFQUUWPZOGYQT-UHFFFAOYSA-O diaminomethylideneazanium;nitrate Chemical compound NC(N)=[NH2+].[O-][N+]([O-])=O MJFQUUWPZOGYQT-UHFFFAOYSA-O 0.000 claims description 38
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims description 24
- 229960001866 silicon dioxide Drugs 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 19
- 238000003860 storage Methods 0.000 claims description 13
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 12
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims description 12
- 229910017604 nitric acid Inorganic materials 0.000 claims description 12
- 239000000523 sample Substances 0.000 claims description 12
- 238000003786 synthesis reaction Methods 0.000 claims description 12
- 239000007858 starting material Substances 0.000 claims description 8
- 239000000047 product Substances 0.000 abstract description 24
- 238000001816 cooling Methods 0.000 abstract description 7
- 238000005516 engineering process Methods 0.000 abstract description 5
- 238000000354 decomposition reaction Methods 0.000 abstract description 3
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 238000007086 side reaction Methods 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract 2
- 239000012295 chemical reaction liquid Substances 0.000 abstract 1
- 239000000706 filtrate Substances 0.000 abstract 1
- 238000004064 recycling Methods 0.000 abstract 1
- 238000000859 sublimation Methods 0.000 abstract 1
- 230000008022 sublimation Effects 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 239000011552 falling film Substances 0.000 description 12
- 229910002804 graphite Inorganic materials 0.000 description 12
- 239000010439 graphite Substances 0.000 description 12
- 239000006096 absorbing agent Substances 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 239000002912 waste gas Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 235000011089 carbon dioxide Nutrition 0.000 description 3
- 238000013022 venting Methods 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- MYFXBBAEXORJNB-UHFFFAOYSA-N calcium cyanamide Chemical compound [Ca+2].[N-]=C=[N-] MYFXBBAEXORJNB-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- CNUNWZZSUJPAHX-UHFFFAOYSA-N guanidine nitrate Chemical compound NC(N)=N.O[N+]([O-])=O CNUNWZZSUJPAHX-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- IDCPFAYURAQKDZ-UHFFFAOYSA-N 1-nitroguanidine Chemical compound NC(=N)N[N+]([O-])=O IDCPFAYURAQKDZ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- STIAPHVBRDNOAJ-UHFFFAOYSA-N carbamimidoylazanium;carbonate Chemical compound NC(N)=N.NC(N)=N.OC(O)=O STIAPHVBRDNOAJ-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N glycolonitrile Natural products N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000003206 sterilizing agent Substances 0.000 description 1
- SEEPANYCNGTZFQ-UHFFFAOYSA-N sulfadiazine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NC1=NC=CC=N1 SEEPANYCNGTZFQ-UHFFFAOYSA-N 0.000 description 1
- 229960004306 sulfadiazine Drugs 0.000 description 1
- BRBKOPJOKNSWSG-UHFFFAOYSA-N sulfaguanidine Chemical compound NC(=N)NS(=O)(=O)C1=CC=C(N)C=C1 BRBKOPJOKNSWSG-UHFFFAOYSA-N 0.000 description 1
- 229960004257 sulfaguanidine Drugs 0.000 description 1
- -1 urea anhydride Chemical class 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a one-step safety production method of guanidine nitrate. The guanidine nitrate product is prepared through the following steps: adding ammonium nitrate, urea and a catalyst which is silicon dioxide or inorganic silica gel or aluminum oxide into a reaction kettle, heating to ensure that urea and ammonium nitrate are molten; controlling the temperature of the reaction liquid in the reaction kettle to maintain a reaction at the temperature; and cooling after the reaction, adding process water, heating the solution, performing hot filtering, recycling the catalyst, cooling the filtrate, filtering out a wet product, and drying the wet product to obtain the finished guanidine nitrate product. Ammonium nitrate is excess, thus urea can be completely reacted, side reactions such as the polymerization or sublimation of urea and decomposition can be reduced, the product yield can be increased and simultaneously the product quality can be increased. The production method has safety; and in order to ensure that the reaction has higher safety, the reaction kettle is connected with a temperature-pressure integrated fire device. The content of the obtained guanidine nitrate can meet the standard of the high-class product. The method has the advantages of simple technology and cheap and common raw material, and is economical and efficient.
Description
Technical field
The present invention relates to a kind of working method of Guanidinium nitrate, particularly the safety in production method of single stage method nitric acid synthesis guanidine belongs to chemical field.
Background technology
Guanidinium nitrate is a kind of broad-spectrum industrial chemicals, and it is a raw material of producing sulfa drugs such as sulfanilylguanidine, Sulphadiazine Sodium and explosive nitroguanidine, also is used to produce Guanidinium carbonate and other guanidinesalt and aspects such as paint industry, photographic material and sterilizing agent.Because the light and heat amount that Guanidinium nitrate sends is few, as propellant its special value is arranged.The method for making various countries of Guanidinium nitrate are different, and the Japan and the U.S. are with the preparation of Dyhard RU 100 method, and Germany adopts direct method to be produced by urea anhydride.Which kind of method no matter, initial raw material has all left not nitrolime.Because the nitrolime industrial scale is little, has limited the production of guanidinesalt.The working method that the Dyhard RU 100 method is produced Guanidinium nitrate is relatively simple, because the Dyhard RU 100 market value than higher, causes the production cost of Dyhard RU 100 method production Guanidinium nitrate than higher.CN1673204A discloses the complete processing of the special-purpose ultra-fine Guanidinium nitrate of a kind of car safety air bag, may further comprise the steps: the Guanidinium nitrate raw material is carried out preliminary mechanical disintegration, obtain granularity less than the first powder of 200 purpose Guanidinium nitrates; With Guanidinium nitrate powder input high pressure fluidized bed jet mill pulverizing just, obtain Guanidinium nitrate one-level fine powder material; Weight ratio by 0.4%-0.9% is added the anti-caking agent in the Guanidinium nitrate fine powder material that last step obtains, and mixes; With last mixed in step the Guanidinium nitrate fine powder material of anti-caking agent drop into disk-type jet mill and disperse, obtain ultra-fine Guanidinium nitrate finished product.For how making Guanidinium nitrate raw material cheaply is easy to get above technology aborning, operation steps is simple and safe, does not provide concrete guidance program.
Summary of the invention
Technical problem to be solved by this invention is, a kind of safety in production method of single stage method nitric acid synthesis guanidine is provided, and this preparing method's raw material cheaply is easy to get, and operation steps is simple and safe, economical and efficient.
For solving the problems of the technologies described above, the technical scheme that the present invention adopts is following:
The safety in production method of single stage method nitric acid synthesis guanidine; Its technical scheme is; It is to process the Guanidinium nitrate product through following process successively: 1. in reaction kettle, add raw material an ammonium nitrate and urea and catalyzer silicon-dioxide or inorganic silica gel or aluminum oxide; The ratio of the weight of used urea, an ammonium nitrate, catalyzer is 1:1.0 ~ 2.0:0.1 ~ 0. 2, and heating makes raw material urea and an ammonium nitrate become molten liquid; 2. control the interior reacting liquid temperature of reaction kettle between 180 ~ 220 ℃, and kept this thermotonus 1 ~ 6 hour; 3. after reaction finishes, be cooled to 170 ~ 100 ℃, add process water; Urea adds that both the weight sums of an ammonium nitrate and the ratio of the weight of process water are 1:1 ~ 3, solution is heated to 100 ℃, heat filtering; Reclaim catalyzer; Again filtrating is cooled to 30 ~ 0 ℃, filters out wet article, wet article obtain the Guanidinium nitrate product through drying.
The safety in production method of above-mentioned single stage method nitric acid synthesis guanidine; Its preferred version is; It is to process the Guanidinium nitrate product through following process successively: 1. in reaction kettle, add raw material an ammonium nitrate and urea and catalyzer silicon-dioxide or inorganic silica gel or aluminum oxide; The ratio of the weight of used urea, an ammonium nitrate, catalyzer is 1:1.5:0.15, and heating makes raw material urea and an ammonium nitrate become molten liquid; 2. control the interior reacting liquid temperature of reaction kettle between 195 ~ 205 ℃, and kept this thermotonus 2.5 ~ 4 hours; 3. after reaction finishes, be cooled to 160 ~ 150 ℃, add process water; Urea adds that both the weight sums of an ammonium nitrate and the ratio of the weight of process water are 1:1 ~ 1.5, solution is heated to 100 ℃, heat filtering; Reclaim catalyzer; Again filtrating is cooled to 20 ~ 25 ℃, filters out wet article, wet article obtain the Guanidinium nitrate product through drying.
In the technique scheme; Preferably connect temperature and pressure interlock fire protection system on the described reaction kettle, the hygrosensor that temperature and pressure interlock fire protection system can have a kettle cover top that is installed on reaction kettle be connected with pressure detector, fire alarm control unit, its water-in hydrant SV, its water-in connection SV water outlet force (forcing) pump, make the starter gear that SV is connected with force (forcing) pump, fire-fighting medium storage tank, solenoid electric valve, the shower nozzle that is connected with the water outlet of force (forcing) pump; The fire-fighting medium storage tank is positioned at the top of reaction kettle; The liquid outlet of fire-fighting medium storage tank is connected with shower nozzle through solenoid electric valve; Shower nozzle adds the hand-hole flange with the fire-fighting medium of reaction kettle kettle cover top and is connected; The temp probe of hygrosensor, the pressure probe of pressure detector all stretch into interior 20 ~ 30 centimetres of reaction kettle; The signal outlet line of hygrosensor and the signal outlet line of pressure detector are connected to the signal input connector of fire alarm control unit respectively, and the signal output part of fire alarm control unit is connected with SV, solenoid electric valve respectively.
The present invention be a kind of be raw material with urea and an ammonium nitrate; The preparation method of nitric acid synthesis guanidine in the presence of catalyzer; Promptly in reaction kettle, add raw material an ammonium nitrate and urea and catalyzer silicon-dioxide or inorganic silica gel or aluminum oxide, heating makes raw material urea and an ammonium nitrate become molten liquid; Reacting liquid temperature in the control reaction kettle, and keep this thermotonus; After reaction finished, cooling added process water, and with the solution heating, heat filtering reclaims catalyzer, and the cooling of will filtrating again filters out wet article, and wet article obtain the Guanidinium nitrate product through drying.In this working method, the weight ratio of used urea and an ammonium nitrate is 1:1.0 ~ 2.0, and an ammonium nitrate is excessive; Guarantee that urea fully reacts; To reduce urea polymerization or side reactions such as distillation, decomposition, when increasing product yield, improved quality product, yield has reached intended purposes.The present invention has replaced two cyanogen ammoniums with urea, has improved Guanidinium nitrate content and yield, has reduced the intermediary operation link, adopts reaction to finish directly to add crystal's system in the afterreaction still, and single stage method is processed high yield high purity Guanidinium nitrate.This working method (three steps) itself has security; Simultaneously, have more security, connect (installation) temperature and pressure interlock fire protection system on the reaction kettle, guarantee reaction safety, efficient for guaranteeing reaction.The content of Guanidinium nitrate of the present invention >=98%, yield (productive rate) is 90 ~ 95%, can reach the standard of HG/T3269-2002 " industrial nitric acid guanidine " premium grads.This method operation steps is simple and safe, has advantages such as raw material cheaply is easy to get, economical and efficient.
Description of drawings
The structural representation that Fig. 1 is connected with temperature and pressure interlock fire protection system for reaction kettle among the present invention.
Embodiment
With reference to Fig. 1, chemical reaction of the present invention is a pyroreaction, and an ammonium nitrate, Guanidinium nitrate all belong to hazardous chemical; Reactant is dangerous big; In case presence of fire in the reaction kettle is because of fire-fighting medium is not easy directly to put out a fire, so often attack time is long; The difficulty of putting out a fire to save life and property is big, has increased property damage and hazard level.Therefore adopt special fire service, promptly on reaction kettle, connect temperature and pressure interlock fire protection system (temp autocontrolled in other words conj.or perhaps and temperature-pressure linkage fire protection system, automatic bubble Firefighting System).In a single day like this, overtemperature flash or fire (pyrolytic decomposition burning) taking place in the reaction kettle, be harm reduction degree to greatest extent, adopts the method cooling and the fire extinguishing of directly fire-fighting medium being injected reaction kettle.Above-mentioned temperature and pressure interlock fire protection system has hygrosensor (temp probe) 21 and the pressure detector (pressure probe) 22 of the kettle cover top that is installed on reaction kettle 1; Fire alarm control unit 3; Its water-in connects the SV 4 of (outside) hydrant A; Its water-in connects the force (forcing) pump (PWR PLT) 6 of the water outlet of SV 4; The starter gear 5 that SV 4 is connected with force (forcing) pump 6; (foam) fire-fighting medium storage tank 7 that is connected with the water outlet of force (forcing) pump 6; Solenoid electric valve 8; Shower nozzle 9 (and signal cable).Fire-fighting medium storage tank 7 is positioned at the top of reaction kettle; The liquid outlet of fire-fighting medium storage tank 7 is connected with shower nozzle 9 through solenoid electric valve 8; Shower nozzle 9 adds the hand-hole flange with the fire-fighting medium of reaction kettle kettle cover top and is connected; The pressure probe of the temp probe of hygrosensor 21, pressure detector 22 all stretches into interior 20 ~ 30 centimetres of reaction kettle; The signal outlet line of hygrosensor 21 and the signal outlet line of pressure detector 22 are connected to the signal input connector of fire alarm control unit 3 respectively, and the signal output part of fire alarm control unit 3 is connected with SV 4, solenoid electric valve 8 respectively.Fire-fighting medium in the above-mentioned fire-fighting medium storage tank 7 can be chemical fire foam (MP).9 in above-mentioned hygrosensor 21 and pressure detector 22, fire alarm control unit 3, SV 4, force (forcing) pump (PWR PLT) 6, starter gear 5, fire-fighting medium storage tank 7, solenoid electric valve 8, shower nozzle are as prior art.(to surpass the temperature alarming value is 206 ℃ such as being provided with when reactor temperature or pressure surpass temperature, pressure set points; The overpressure alarming value is gauge pressure 0.1MPa) time; Temp probe and pressure probe are sent to fire alarm control unit 3 with data, and fire alarm control unit 3 can be set at automatic catch 31 or manually keep off 32.When being made as automatic catch 31, fire alarm control unit 3 starts SV 4 automatically, and hydrant is started; Cause starter gear 5 responses simultaneously; Starter gear 5 starts force (forcing) pump (PWR PLT) 6, and the water flows in the fire-fighting medium storage tank 7 produces vacuum and drives fire-fighting medium, through the solenoid electric valve 8 that has been started by fire alarm control unit 3; Through shower nozzle 9 (fire-fighting) fire-fighting medium is directly injected in the reaction kettle, reach the purpose of direct fire extinguishing.When being made as manual retaining 32, after temp probe and pressure probe were sent to fire alarm control unit 3 with data, fire alarm control unit 3 sent sound and light alarm; The site operation personnel thinks and is necessary in reaction kettle, to inject fire-fighting medium; Then press " startup " button on the fire alarm control unit 3, fire alarm control unit 3 starts SV 4, and hydrant is started; Cause starter gear 5 responses simultaneously; Starter gear 5 starts force (forcing) pump (PWR PLT) 6, and the water flows in the fire-fighting medium storage tank 7 produces vacuum and drives fire-fighting medium, through the solenoid electric valve 8 that has been started by fire alarm control unit 3; Through shower nozzle 9 (fire-fighting) fire-fighting medium is directly injected in the reaction kettle, reach the purpose of direct fire extinguishing.
Embodiment 1: the safety in production method of single stage method nitric acid synthesis guanidine, and it is (the principal reaction formula is a face as follows) of processing the Guanidinium nitrate product successively through following process:
1. in the 5000L reaction kettle, add raw material an ammonium nitrate 1500Kg and urea 1000Kg and catalyzer silicon-dioxide or inorganic silica gel or aluminum oxide (aluminium sesquioxide) 150Kg, the catalyzer of selecting in the present embodiment is silicon-dioxide (a perhaps aluminum oxide).The ratio of the weight of used urea, an ammonium nitrate, catalyzer is 1:1.5:0.15, and heating makes raw material urea and an ammonium nitrate become molten liquid (this moment, fluid temperature was between 170 ~ 175 ℃).2. the reacting liquid temperature in (through heat-transfer medium) control reaction kettle is 200 ℃ (can select 200 ± 5 ℃), and keeps this thermotonus 3 hours.It is 206 ℃ that the overtemperature alarm value is set, and the pressure alarm value is gauge pressure 0.1MPa.3. begin cooling after reaction finishes, be cooled to 160 ℃, (disposable) adds zero(ppm) water (process water) 2500L; In the present embodiment, (urea+an ammonium nitrate): process water is 1:1 (ratio of weight), and solution is heated to 100 ℃; Heat filtering reclaims catalyzer, again filtrating is cooled to 25 ℃; Filter out wet article, wet article obtain Guanidinium nitrate (making with extra care) product 955Kg through drying.(making with extra care) product content is 98.2%, and yield (productive rate) is 93% (with ureometer).
Aforesaid reaction vessel is connected with three grades of graphite falling film absorbers (graphite falling film absorption device) through water ring vacuum pump; In the Guanidinium nitrate synthetic reaction process, there are waste gas carbonic acid gas and ammonia to emit; The venting hole of reaction kettle is connected with three grades of graphite falling film absorbers; Through water ring vacuum pump the waste gas that produces is introduced absorption back emptying in three grades of graphite falling film absorbers, absorption strength reaches at 10 ~ 15% o'clock, is replaced by new water.This is a prior art.
Embodiment 2: the safety in production method of single stage method nitric acid synthesis guanidine; It is (the principal reaction formula is seen embodiment 1) of processing the Guanidinium nitrate product successively through following process: 1. in the 5000L reaction kettle, add raw material an ammonium nitrate 1000Kg and urea 1000Kg and catalyzer silicon-dioxide or inorganic silica gel or aluminum oxide (aluminium sesquioxide) 150Kg, the catalyzer of selecting in the present embodiment is aluminum oxide (a perhaps silicon-dioxide).The ratio of the weight of used urea, an ammonium nitrate, catalyzer is 1:1:0.15, and heating makes raw material urea and an ammonium nitrate become molten liquid (this moment, fluid temperature was between 170 ~ 175 ℃).2. the reacting liquid temperature in (through heat-transfer medium) control reaction kettle is 190 ℃ (can select 190 ± 5 ℃), and keeps this thermotonus 5 hours.It is 206 ℃ that the overtemperature alarm value is set, and the pressure alarm value is gauge pressure 0.1MPa.3. begin cooling after reaction finishes, be cooled to 160 ℃, (disposable) adds zero(ppm) water (process water) 3000L; In the present embodiment, (urea+an ammonium nitrate): process water is 1:1.5 (ratio of weight), and solution is heated to 100 ℃; Heat filtering reclaims catalyzer, again filtrating is cooled to 25 ℃; Filter out wet article, wet article obtain Guanidinium nitrate (making with extra care) product 932Kg through drying.(making with extra care) product content is 98.5%, and yield (productive rate) is 91% (with ureometer).
Aforesaid reaction vessel is connected with three grades of graphite falling film absorbers (graphite falling film absorption device) through water ring vacuum pump; In the Guanidinium nitrate synthetic reaction process, there are waste gas carbonic acid gas and ammonia to emit; The venting hole of reaction kettle is connected with three grades of graphite falling film absorbers; Through water ring vacuum pump the waste gas that produces is introduced absorption back emptying in three grades of graphite falling film absorbers, absorption strength reaches at 10 ~ 15% o'clock, is replaced by new water.This is a prior art.
Embodiment 3: the safety in production method of single stage method nitric acid synthesis guanidine; It is (the principal reaction formula is seen embodiment 1) of processing the Guanidinium nitrate product successively through following process: 1. in reaction kettle, add raw material an ammonium nitrate and urea and catalyzer silicon-dioxide or inorganic silica gel or aluminum oxide, the catalyzer of selecting in the present embodiment is inorganic silica gel (a perhaps silicon-dioxide).The ratio of the weight of used urea, an ammonium nitrate, catalyzer is 1:2.0:0. 2 (perhaps 1:1.2:0.1), and heating makes raw material urea and an ammonium nitrate become molten liquid.2. control the interior reacting liquid temperature of reaction kettle at 180 ℃ (perhaps 220 ℃), and kept this thermotonus 1 hour (perhaps 6 hours).It is 206 ℃ that the overtemperature alarm value is set, and the pressure alarm value is gauge pressure 0.1MPa.3. after reaction finishes, be cooled to 170 ℃ (perhaps 100 ℃), add process water; Urea adds that both the weight sums of an ammonium nitrate and the ratio of the weight of process water are 1:3, solution is heated to 100 ℃, heat filtering; Reclaim catalyzer; Again filtrating is cooled to 5 ℃, filters out wet article, wet article obtain the Guanidinium nitrate product through drying.Product content is 98.1%, and yield (productive rate) is 91.5% (with ureometer).
Aforesaid reaction vessel is connected with three grades of graphite falling film absorbers (graphite falling film absorption device) through water ring vacuum pump; In the Guanidinium nitrate synthetic reaction process, there are waste gas carbonic acid gas and ammonia to emit; The venting hole of reaction kettle is connected with three grades of graphite falling film absorbers; Through water ring vacuum pump the waste gas that produces is introduced absorption back emptying in three grades of graphite falling film absorbers, absorption strength reaches at 10 ~ 15% o'clock, is replaced by new water.This is a prior art.
More than its content of Guanidinium nitrate of obtaining among each embodiment can reach the standard of HG/T3269-2002 " industrial nitric acid guanidine " premium grads.This method technology is simple, and raw material cheaply is easy to get, economical and efficient.
Above embodiment is used to further specify the present invention, but does not limit the present invention in any form.
Claims (3)
1. the safety in production method of single stage method nitric acid synthesis guanidine; It is characterized in that it is to process the Guanidinium nitrate product through following process successively: 1. in reaction kettle, add raw material an ammonium nitrate and urea and catalyzer silicon-dioxide or inorganic silica gel or aluminum oxide; The ratio of the weight of used urea, an ammonium nitrate, catalyzer is 1:1.0 ~ 2.0:0.1 ~ 0. 2, and heating makes raw material urea and an ammonium nitrate become molten liquid; 2. control the interior reacting liquid temperature of reaction kettle between 180 ~ 220 ℃, and kept this thermotonus 1 ~ 6 hour; 3. after reaction finishes, be cooled to 170 ~ 100 ℃, add process water; Urea adds that both the weight sums of an ammonium nitrate and the ratio of the weight of process water are 1:1 ~ 3, solution is heated to 100 ℃, heat filtering; Reclaim catalyzer; Again filtrating is cooled to 30 ~ 0 ℃, filters out wet article, wet article obtain the Guanidinium nitrate product through drying.
2. the safety in production method of single stage method nitric acid synthesis guanidine according to claim 1; It is characterized in that it is to process the Guanidinium nitrate product through following process successively: 1. in reaction kettle, add raw material an ammonium nitrate and urea and catalyzer silicon-dioxide or inorganic silica gel or aluminum oxide; The ratio of the weight of used urea, an ammonium nitrate, catalyzer is 1:1.5:0.15, and heating makes raw material urea and an ammonium nitrate become molten liquid; 2. control the interior reacting liquid temperature of reaction kettle between 195 ~ 205 ℃, and kept this thermotonus 2.5 ~ 4 hours; 3. after reaction finishes, be cooled to 160 ~ 150 ℃, add process water; Urea adds that both the weight sums of an ammonium nitrate and the ratio of the weight of process water are 1:1 ~ 1.5, solution is heated to 100 ℃, heat filtering; Reclaim catalyzer; Again filtrating is cooled to 20 ~ 25 ℃, filters out wet article, wet article obtain the Guanidinium nitrate product through drying.
3. the safety in production method of single stage method nitric acid synthesis guanidine according to claim 1 and 2; It is characterized in that on the aforesaid reaction vessel connecting temperature and pressure interlock fire protection system, the hygrosensor that temperature and pressure interlock fire protection system has a kettle cover top that is installed on reaction kettle be connected with pressure detector, fire alarm control unit, its water-in hydrant SV, its water-in connection SV water outlet force (forcing) pump, make the starter gear that SV is connected with force (forcing) pump, fire-fighting medium storage tank, solenoid electric valve, the shower nozzle that is connected with the water outlet of force (forcing) pump; The fire-fighting medium storage tank is positioned at the top of reaction kettle; The liquid outlet of fire-fighting medium storage tank is connected with shower nozzle through solenoid electric valve; Shower nozzle adds the hand-hole flange with the fire-fighting medium of reaction kettle kettle cover top and is connected; The temp probe of hygrosensor, the pressure probe of pressure detector all stretch into interior 20 ~ 30 centimetres of reaction kettle; The signal outlet line of hygrosensor and the signal outlet line of pressure detector are connected to the signal input connector of fire alarm control unit respectively, and the signal output part of fire alarm control unit is connected with SV, solenoid electric valve respectively.
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| CN111249650A (en) * | 2019-12-27 | 2020-06-09 | 山西北化关铝化工有限公司 | Instantaneous fire extinguishing and explosion suppression system for explosive production |
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Application publication date: 20120411 |