CN103145587A - Method for synthesizing powdered nitric acid by using allantoin synthetic waste liquid - Google Patents
Method for synthesizing powdered nitric acid by using allantoin synthetic waste liquid Download PDFInfo
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- CN103145587A CN103145587A CN2012105933063A CN201210593306A CN103145587A CN 103145587 A CN103145587 A CN 103145587A CN 2012105933063 A CN2012105933063 A CN 2012105933063A CN 201210593306 A CN201210593306 A CN 201210593306A CN 103145587 A CN103145587 A CN 103145587A
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Abstract
The invention discloses a method for synthesizing powdered nitric acid by using allantoin synthetic waste liquid. A preparation process is that 40%-50% of percentage concentration by weight of allantoin synthetic waste liquid is added in a reactor for cooling until the temperature is lower than 5 DEG C, 50%-65% of percentage concentration by weight of dilute nitric acid is added during stirring, a molar ratio of nitric acid to urea in reaction liquid is controlled to be 1:0.9-1.1 during material adding, the temperature of the reaction liquid is controlled to be below 20 DEG C, materials are reacted for 0.5-2.0 hours at the temperature of 15 DEG C after material adding is completed, the reaction liquid is cooled to the temperature below 5 DEG C, centrifugal separation is carried out to separate out crystallization, vacuum drying is carried out on the crystallization at the temperature of 50 DEG C, and powdered nitric acid products are obtained. The nitric acid content in the products is 48%-50%, and the allantoic acid impurity content in the products is 3%-5%.
Description
Technical field
The present invention relates to a kind of powder nitric acid synthetic method, particularly with the method for the synthetic waste liquid synthetic powder nitric acid of wallantoin, belong to petrochemical complex and field of environment protection.
Background technology
Sell in the market a kind of powder nitric acid, its chemical composition is actually urea nitrate, is obtained theoretical nitric acid content 51.2% in product by nitric acid and the reaction of urea equimolar ratio, set out for transportation and storage security needs, the urea nitrate industrial goods often contain the moisture of 10% left and right.Be solid-state under urea nitrate normal temperature, water-soluble rear aobvious acidity, its acidity is slightly low than nitric acid, and its chemical stability is better, and itself does not have corrodibility solid phase prod, can replace nitric acid to use in a lot of occasions, and makes up the deficiency of liquid nitric acid.
English Patent GB1109619 (1966-04-29) discloses the urea nitrate preparation method the earliest, makes nitric acid and urea reaction with same mole, temperature of reaction 105-135 ℃, but temperature of reaction when too high urea nitrate can decompose in a large number, yield drops to 91%." Tianjin chemical industry " magazine 2009, the 2nd phase, the 42-44 page has been reported the preparation method of urea nitrate, under optimal conditions, nitric acid and the reaction of urea equimolar ratio, temperature of reaction 20-70 ℃, the highest yield of urea nitrate reaches 74.88%.Chinese patent CN1583716 (2005-02-23) discloses a kind of manufacture method of non-active nitric acid powder, the mol ratio of nitric acid and urea 1: 1.05, and reacts under acetate/acetic buffer reagent existence condition, extrapolates urea nitrate yield 77.2%.
Powder nitric acid is mainly used in the oil-field development acidization at present, and Chinese patent CN102382637 (2012-03-12) discloses a kind of water-based carrying non-active nitric acid powder and manufacture method thereof; Powder nitric acid can be used as slow release fertilizer, and Chinese patent CN102491858 (2012-06-13) discloses the manufacture method of the basic slow-release compound fertilizer of a kind of nitre urine; Powder nitric acid can be used as the civil safety explosive, and Chinese patent CN1431182 (2003-07-23) discloses a kind of safety firworks string roasting and boiling as two means of processing crude drugs agent composition; Powder nitric acid can be used as medicine chemical material, and Chinese patent CN101591261 (2009-12-02) discloses a kind of L-2, the synthetic method of 4-dinitrobenzene L-Ala; Powder nitric acid can be used as clean-out system, easily and efficiently oxide compound and the fouling on boiler rinsing, interchanger, pipeline and sanitary ware.
Powder nitric acid is compared with liquid nitric acid, and the advantage of safe and convenient is very outstanding in transportation, storage and use procedure, due to the Cost Problems of raw material nitric acid and urea, causes product price higher, has limited to a certain extent its widespread use.Adopting urea or nitric acid production powder nitric acid in medication chemistry by product and waste material is the effective way that reduces production costs.
Wallantoin is widely used in the fields such as medicine, daily-use chemical industry and agricultural, and wallantoin technique is produced in main employing oxoethanoic acid and urea condensation under mineral acid catalysis both at home and abroad, the general urea raw material that drops into excessive a times in production.German patent DE 1939924 (1971-02-18) discloses mineral acid and has catalyzed and synthesized wallantoin technique, and synthesis yield is less than 60%.Present domestic wallantoin industrial scale has reached 2000 tons, and industrial scale constantly enlarges, but enterprise's wallantoin production actual production yield 40%-55% only, the acid waste liquor that contains high concentration urea is difficult to process, cause serious environmental pollution, limited the production-scale expansion of wallantoin.Chinese patent CN102060392 (2011-05-18) discloses a kind of with the synthetic corrosion-mitigation scale-inhibition agent method of wallantoin waste liquid, but recycles the technique more complicated, needs to increase specific equipment.
When powder nitric acid uses as oil-field development souring agent or interchanger clean-out system, product cost is crucial, if wherein exist a small amount of wallantoin or organic impurity little to using influential effect, urea synthesis powder nitric acid in comprehensive utilization wallantoin synthesis mother liquid, not only the powder nitric acid production cost can be reduced, and environmental pollution can be alleviated.
Summary of the invention
The purpose of this invention is to provide a kind of method of utilizing the synthetic waste liquid synthetic powder nitric acid of wallantoin, pollute to reduce the powder nitric acid production cost and to alleviate the wallantoin production environment.
Wallantoin building-up reactions more complicated; it is generally acknowledged that reaction is proceed step by step; at first be that an oxoethanoic acid molecule and two urea molecules carry out condensation reaction generation allantoic acid under acid catalysis; then an aminoacyl in carboxyl and urea groups changes into ring and generates wallantoin, and chemical equation is as follows:
In order to improve the wallantoin synthesis yield, require raw material urea greatly excessive, usually oxoethanoic acid and urea molar ratio are 1: 3.5-4.5, about 50% the unconverted urea that utilizes of residue in reaction mother liquor, by product are mainly the allantoic acids of Cheng Huan not.
Under normal temperature, solubleness is less than 1% in the aqueous solution for wallantoin, and urea is solubleness 50% in the aqueous solution, and allantoic acid is also soluble in water, can not be from synthesis mother liquid under the urea normal temperature of unconverted utilization during wallantoin is synthetic Crystallization Separation out.
Have the amino group of high degree of polarization in urea molecule, wherein in the N atom, unpaired electronics is arranged, it and strong acid effect generate salt.Experiment find ureasulfuric acid and urea hydrochloride soluble in water, and urea nitrate solubleness approximately 10% in the aqueous solution, and reduce with temperature and descend, this is the theoretical basis of nitric acid synthesis urea (powder nitric acid).
The synthetic waste liquid of wallantoin derives from the mother liquor with oxoethanoic acid and urea synthetic allantoin under mineral acid catalysis, contains unconverted urea, a small amount of wallantoin, allantoic acid by product, sulfuric acid, hydrochloric acid or nitric acid catalyzer in mother liquor.When making catalyzer with nitric acid, in mother liquor, urea and nitric acid all can fully utilize.First waste liquid is concentrated into weight percent concentration 40%-50% when mother liquid concentration is too low.
Experiment finds that the solubleness of powder nitric acid in the synthetic waste liquid of wallantoin is not only relevant with temperature, and relevant with other by-product concentration with mother liquor acidity.There is essence different with the synthetic waste liquid synthetic powder nitric acid of wallantoin from disclosed processing condition with industrial raw material synthetic powder nitric acid.Experiment finds that when temperature of reaction is too high, the powder nitric acid of generation is clamminess, and product is difficult to separate and is dry, and in product, nitric acid content is on the low side, may be that in mother liquor, by product and urea nitrate react and cause.
Experiment finds that in the synthetic waste liquid of wallantoin, by product promotes that powder nitric acid crystallizes out, and the allantoic acid by product has corrosion and scale inhibition performance, can improve to a certain extent powder nitric acid as the application performance of souring agent and clean-out system.
Technical scheme and concrete measure that the present invention takes are:
The synthetic waste liquid of wallantoin is concentrated into weight percent concentration 40%-50%; The synthetic waste liquid of the wallantoin of weight percent concentration 40%-50% is added in reactor, below cooling reaction solution to 5 ℃; The rare nitric acid that under agitation adds weight percent concentration 50%-65% controls when feeding intake that in reaction solution, the mol ratio of nitric acid and urea is 1: 0.9-1.1; Control reacting liquid temperature when feeding intake below 20 ℃, occur to reduce side reaction; Feed intake complete after at 15 ℃ of insulation reaction 0.5-2.0 hours, below cooling reaction solution to 5 ℃, the crystallization that centrifugation is separated out; Crystallization is obtained the powder nitric acid product 50 ℃ of lower vacuum-dryings, nitric acid content 48%-50% and allantoic acid foreign matter content 3%-5% in product.
In product of the present invention, nitric acid content is measured and is adopted spectrophotometry, namely take Pbenoldisulfonic Acid as developer, measures the absorbancy that contains nitrate compound under 410nm, obtains as working curve with the absorbancy of saltpetre standardized solution.
In product of the present invention, the allantoic acid dirt content test adopts acid base titration, namely makes the indicator titration total acid content with methyl red, deducts the nitric acid content reckoning and obtains.
Advantage of the present invention and beneficial effect are: the synthetic waste liquid synthetic powder nitric acid of comprehensive utilization wallantoin, not only reduced the powder nitric acid production cost, and alleviated the problem of the environmental pollution in the wallantoin building-up process; The powder nitric acid that the synthetic waste liquid of wallantoin makes only contains a small amount of organic impurity, can be used as oil-field development souring agent or heat-exchange equipment clean-out system and uses.
Embodiment
Embodiment 1
In the 500mL four-hole reaction flask of mechanical stirrer, thermometer, dropping funnel, reflux condensing tube is housed, add urea 120g (2.0mol), deionized water 200mL and 50% sulfuric acid 183g.Be heated to 60-70 ℃ with water-bath, add 40.2% industrial oxoethanoic acid 92g (0.5mol) in 0.5 hour, stirring reaction made reaction carry out fully in 4 hours.Reactant is cooled to 20 ℃, centrifugation, washs, obtain the wet product of wallantoin.The wallantoin synthesis mother liquid is 500g approximately, and wherein urea accounts for 60g (1.0mol), sulfuric acid 92g, and the allantoic acid by product is 40g approximately.
with the mother liquor vacuum concentration to about half volume, pack in 500mL four-hole reaction flask, be cooled to below 5 ℃ with frozen water, the rare nitric acid 97g (1.0mol) that under agitation slowly adds weight percent concentration 65%, constantly there is the urea nitrate white crystals to separate out, feed intake the control temperature of reaction below 20 ℃, insulation reaction 1 hour, below further cooling reaction solution to 5 ℃, the crystallization that centrifugation is separated out, and with a small amount of cold water washing crystallization, obtain white powder nitric acid 114g 50 ℃ of lower vacuum-dryings after drying, nitric acid content 48.5% and allantoic acid foreign matter content 3.2% in product.
Embodiment 2
In the 500mL four-hole reaction flask of mechanical stirrer, thermometer, dropping funnel, reflux condensing tube is housed, add urea 120g (2.0mol), 31% concentrated hydrochloric acid 200mL and 40.2% industrial oxoethanoic acid 92g (0.5mol), use heating in water bath, stirred 4 hours under 60-70 ℃, make condensation reaction solution be cooled to 20 ℃, centrifugation, wash, obtain the wet product of wallantoin.The wallantoin synthesis mother liquid is 350g approximately, and wherein urea accounts for 61g (1.0mol), hydrochloric acid 62g, and the allantoic acid by product is 35g approximately.
with the mother liquor vacuum concentration to about half volume, pack in 500mL four-hole reaction flask, be cooled to below 5 ℃ with frozen water, the rare nitric acid 97g (1.0mol) that under agitation slowly adds weight percent concentration 65%, constantly there is the urea nitrate white crystals to separate out, feed intake the control temperature of reaction below 20 ℃, insulation reaction 0.5 hour, below further cooling reaction solution to 5 ℃, the crystallization that centrifugation is separated out, and with a small amount of cold water washing crystallization, obtain white powder nitric acid 116g 50 ℃ of lower vacuum-dryings after drying, nitric acid content 49% and allantoic acid foreign matter content 3% in product.
Embodiment 3
In the 500mL four-hole reaction flask of mechanical stirrer, thermometer, dropping funnel, reflux condensing tube is housed, add urea 120g (2.0mol), deionized water 200mL, 50% nitric acid 50mL and 40.2% industrial oxoethanoic acid 92g (0.5mol), use heating in water bath, stirred 4 hours under 60-70 ℃, make condensation reaction solution be cooled to 20 ℃, centrifugation, wash, obtain the wet product of wallantoin.The wallantoin synthesis mother liquid is 400g approximately, and wherein urea accounts for 63g (1.05mol), nitric acid 32g, and the allantoic acid by product is 30g approximately.
with the mother liquor vacuum concentration to about half volume, pack in 500mL four-hole reaction flask, be cooled to below 5 ℃ with frozen water, there is a small amount of urea nitrate white crystals to separate out, the rare nitric acid 48.5g (0.5mol) that under agitation slowly adds weight percent concentration 65%, feed intake the control temperature of reaction below 20 ℃, insulation reaction 0.5 hour, below further cooling reaction solution to 5 ℃, the crystallization that centrifugation is separated out, and with a small amount of cold water washing crystallization, obtain white powder nitric acid 120g 50 ℃ of lower vacuum-dryings after drying, nitric acid content 49.5% and allantoic acid foreign matter content 3.5% in product.
Claims (1)
1. a synthetic powder method of nitric acid, is characterized in that fully utilizing urea and nitric acid synthetic powder nitric acid in the synthetic waste liquid of wallantoin, reduces powder nitric acid production cost and the environmental pollution that alleviates in the wallantoin building-up process, and building-up process comprises the following steps:
(1) the synthetic waste liquid of wallantoin is concentrated into weight percent concentration 40%-50%;
(2) the synthetic waste liquid of wallantoin is added in reactor, be cooled to below 5 ℃;
(3) under agitation add rare nitric acid of weight percent concentration 50%-65% in the synthetic waste liquid of wallantoin, control when feeding intake that in reaction solution, the mol ratio of nitric acid and urea is 1: 0.9-1.1;
Control reacting liquid temperature when (4) feeding intake below 20 ℃, feed intake complete after at 15 ℃ of insulation reaction 0.5-2.0 hours, below cooling reaction solution to 5 ℃, the crystallization that centrifugation is separated out;
(5) crystallization is obtained the powder nitric acid product 50 ℃ of lower vacuum-dryings, nitric acid content 48%-50% and allantoic acid foreign matter content 3%-5% in product.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3330864A (en) * | 1965-04-29 | 1967-07-11 | Conversion Chem Corp | Method for making urea nitrate |
| DE1939924B2 (en) * | 1969-08-06 | 1977-10-13 | Basf Ag, 6700 Ludwigshafen | PROCESS FOR THE PREPARATION OF ALLANTOIN IN AQUATIC MEDIUM |
| CN1424377A (en) * | 2002-12-24 | 2003-06-18 | 山东省滨州天欧机化有限责任公司 | Nitric acid powder and liquid production |
| CN1583716A (en) * | 2004-06-14 | 2005-02-23 | 陕西福奥特实业有限公司 | Preparing method for inactive nitric acid powder |
-
2012
- 2012-12-27 CN CN2012105933063A patent/CN103145587A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3330864A (en) * | 1965-04-29 | 1967-07-11 | Conversion Chem Corp | Method for making urea nitrate |
| DE1939924B2 (en) * | 1969-08-06 | 1977-10-13 | Basf Ag, 6700 Ludwigshafen | PROCESS FOR THE PREPARATION OF ALLANTOIN IN AQUATIC MEDIUM |
| CN1424377A (en) * | 2002-12-24 | 2003-06-18 | 山东省滨州天欧机化有限责任公司 | Nitric acid powder and liquid production |
| CN1583716A (en) * | 2004-06-14 | 2005-02-23 | 陕西福奥特实业有限公司 | Preparing method for inactive nitric acid powder |
Non-Patent Citations (2)
| Title |
|---|
| 袁吉: "合成尿囊素的一种简化方法", 《贵州化工》 * |
| 陈颖超，王光龙: "硝酸脲的制备", 《天津化工》 * |
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Application publication date: 20130612 |