CN1597500A - Two-step preparation technology of amino sulfonic acid - Google Patents
Two-step preparation technology of amino sulfonic acid Download PDFInfo
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- CN1597500A CN1597500A CN 03159539 CN03159539A CN1597500A CN 1597500 A CN1597500 A CN 1597500A CN 03159539 CN03159539 CN 03159539 CN 03159539 A CN03159539 A CN 03159539A CN 1597500 A CN1597500 A CN 1597500A
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Abstract
A two-step process for preparing aminosulfonic acid from SO3 gas generated by sulfuric acid plant features that the fire step features high reaction temp and limited addition of SO3 and the second step features low reaction temp and addition of sufficient SO3, resulting in high safety and low cost.
Description
Technical field the present invention relates to a kind of preparation technology of thionamic acid, and relating in particular to a kind of is raw material with urea, sulfuric acid and sulphur trioxide, and two step method prepares the improvement technology of dry product thionamic acid.
The preparation method of background technology thionamic acid has multiple, as solvent cooling method, sulfan overflow method, solid solvents method, two step method etc.The solvent cooling method is to attempt to vaporize by solvent---condensation, come dissipation reaction heat, thus the carrying out of control reaction.United States Patent (USP) 4,386,060 discloses a kind of method, promptly adopts fluorochlorohydrocarbon as solvent, and direct production content reaches 92% dry product thionamic acid, but the product colour yellowing, and the fluorochlorohydrocarbon use that will be under an embargo in 2005, so there has not been realistic meaning.
The sulfan overflow method is reactant urea and sulfuric acid to be put into a large amount of sulfans react, and sulfan is as a kind of liquid solvent of reaction, with the carrying out of dissipation reaction heat and control reaction, as United States Patent (USP) 2,408,823.Reach 92% dry product thionamic acid though this method can be produced content, because sulfan costs an arm and a leg, the production cost height is difficult to bear economically.
United States Patent (USP) 2,408,492 disclose a kind of solid solvents method, promptly under the condition that has a large amount of solid solvents to exist, each reactant are deposited in together, and concrete ratio guarantees that reaction mass is apparent drying and does not have any continuous liquid really and exists mutually.This solvent is for the oneself who hinders reaction quickens, and for the release of the gaseous product carbonic acid gas of reaction provides huge surface area, thereby reaches the purpose of control reaction temperature.But the prepared dry product thionamic acid of this method exists foreign matter content height, shortcoming that yield is low.
Two step method is meant that in the first step reaction all reaction mass urea, sulfuric acid and sulphur trioxides at first add the premixed device of a band refrigerating function, and reaction generates a kind of complexing liquid, and then this complexing liquid is heated the generation thionamic acid in second step.As United States Patent (USP) 2,390,648,2,409,572 etc., wherein United States Patent (USP) 2,409, and 572, be an improvement technology on United States Patent (USP) 2,390648 bases, it adopts the interior chuck refrigerative premixed device and of a band to be used for the external cooler of refrigeration cycle slip, realizes the first step reaction.This technology requires strict especially to the control of temperature of reaction, especially when working concentration is higher than 45% oleum, temperature of reaction must be strict controlled in 35 ~ 40 ℃ of scopes, be higher than this temperature range, the formation reaction of thionamic acid speeds up, the growing amount of thionamic acid increases, thereby causes that slip viscosity strengthens; And be lower than this temperature range, then near the temperature of solidification of oleum, slip viscosity also strengthens thereupon, data show that be lower than 6 ℃ of this temperature ranges, slip viscosity will double.As seen no matter be higher or lower than 35 ~ 40 ℃ of scopes, all will make the just bigger slip of former intrinsic viscosity carry difficulty more.In scale operation, certainly will exist conducts heat is difficult to normal, stable carrying out, in case the prolong of external cooler stops up, will cause vicious cycle, the out of control danger of reaction occurs, even the danger of blast occurs.In addition, the same with above-mentioned principle, this technology also has strict especially control requirement to the chuck temperature of cooling water, especially can not hang down oleum is solidified.These have not only strengthened the difficulty of red-tape operati, and cause the thionamic acid unstable product quality of producing.
Summary of the invention the present invention is at above-mentioned United States Patent (USP) 2,409, improvement and innovative technology on the 572 two step method process bases, purpose is to provide that a kind of turndown ratio is big, operation easier and operational danger is little, flow process is succinct, and can use low price, the sulphur trioxide reforming gas of the sulfuric acid plant that conveniently is easy to get is as raw material, direct production content is greater than the operational path of 92% dry product thionamic acid.
The present invention has kept United States Patent (USP) 2,409, the technological advantage of 572 direct production high-content dry product thionamic acids, and to its first step reaction improves and innovates.Especially, the first step of the present invention reaction is carried out as follows: continuously whole sulfuric acid or concentration are lower than first still that 38% oleum joins multi-stage reacting kettle, add urea and sulphur trioxide simultaneously, stir and cool off the formation reaction of inhibition thionamic acid, the wherein sulphur trioxide segmentation adding of limiting the quantity of, the first still sulphur trioxide cumulative amount is no more than and adds 75% of sulfuric acid mo1 number, sulfuric acid, urea and three kinds of raw material accumulative total of sulphur trioxide mol ratio are 1: 1: 1.3 ~ 1.6, each still temperature of reaction is set in 70 ~ 25 ℃ of scopes from high to low according to the sulphur trioxide additional proportion.
Described multi-stage reacting kettle is at least 2 stills, and though more tend to safety, stable more than the operation of 4 stills, there is the shortcoming that plant investment is big, floor space is big, energy consumption is high in best 3 ~ 4 stills.
When adopting the above operate continuously of 3 stills, urea also sectional adds, and wherein, the final stage still avoids adding urea, otherwise can not guarantee the abundant complete reaction of urea, thereby influences final thionamic acid quality product.
When adopting 3 still operate continuouslys, first, second and third still sulphur trioxide accumulative total add-on accounts for and adds 0 ~ 75%, 75 ~ 100%, 130 ~ 160% of sulfuric acid mol number, first and second still urea accumulative total add-on accounts for and adds 50 ~ 100%, 100% of sulfuric acid mol number, first, second and third still temperature is controlled at respectively in 25 ~ 70 ℃, 25 ~ 55 ℃, 25 ~ 40 ℃ scopes, the thionamic acid constant product quality that reacting balance carries out and generates.
Foregoing invention is based on such thinking proposition: improve the carrying out that temperature helps urea, sulfuric acid and sulphur trioxide complex reaction, but also quicken the formation reaction of thionamic acid simultaneously, this exactly is again that the first step reaction is undesirable.But no matter be the complex reaction of the first step, or the formation reaction of thionamic acid, its speed of response all is subjected to the sulphur trioxide quantitative limitation, and when the sulphur trioxide consumption increased, this two steps speed of response was all accelerated; Equally, reduce sulphur trioxide consumption in early stage, the thermopositive reaction of the first step gently, suppressing the reaction of second step takes place, at this moment improve temperature and will speed up the carrying out of the first step reaction, but react inviolent, and the formation reaction of the second step thionamic acid does not show acceleration, and because the increasing of heat transfer temperature difference, make reaction be easy to control and not dangerous.Therefore, by the ratio of control sulphur trioxide add-on, improve the first step reaction the carrying out that early stage, temperature was quickened complex reaction, and reaction is mild, the formation reaction of thionamic acid simultaneously is inhibited.Promptly by the adding of limiting the quantity of of the first step comparatively high temps in reaction early stage, sulphur trioxide is set; The late phase reaction temperature is lower, the sulphur trioxide capacity adds, not only reach the purpose that improves the first step speed of response, reduction the first step reaction severity, suppresses the formation reaction of thionamic acid, and because the first step reaction temperature in early stage is higher, help the carrying out and the temperature controlling of conducting heat, also strengthen the turndown ratio of technology, reduced operation easier and operational danger.
The present invention selects chuck refrigerative reactor in the band for use in the use of device, the drop successive reaction mode that flows avoids using shurry pump, tubular(surface)condenser and many valve operations, and flow process is succinct, and is flexible to operation, has improved the safe operation coefficient that installs.
In addition, the inventor is in experiment, discovery can easy to usely be easy to get, one section of sulfuric acid plant with low cost and two sections sulphur trioxide reforming gas substitute sulfans as raw material, produce content greater than 92% dry product thionamic acid, solved direct production high-content dry product thionamic acid and just must working concentration be higher than 45% the oleum or the difficult problem of sulfan.When one section of using sulfated factory and two sections sulphur trioxide reforming gas, must carry out cooling process to it, owing to sulfur trioxide content height in one section reforming gas, the inventory of processing is less relatively, help saving the cooling energy consumption, so the one section sulphur trioxide reforming gas that uses high density is for well.
The present invention compares with the preparation technology of existing two step method thionamic acid, adds and the hydraulic current flowing mode owing to adopt the sulphur trioxide segmentation to limit the quantity of, and has widened the operating restraint of processing parameter, has reduced operation easier and operational danger; Adopt the sulphur trioxide reforming gas of sulfuric acid plant to substitute sulfan, reduced the production cost of thionamic acid significantly as raw material.
Among the embodiment of embodiment the following stated, except that specializing, inventory all is meant weight.
Embodiment 1
The continuous reaction apparatus that is composed in series by two reactors adds first reactor with the oleum of 80 part of 20% concentration per hour, 40 parts urea, the speed of 25 parts of sulfans, stirs and cooling is controlled at 50 ~ 40 ℃ of temperature ranges; Add second reactor with the speed of 35 parts of sulfans per hour again, stir and cooling is controlled at 40 ~ 25 ℃ of temperature ranges; The complex compound that reaction generates, is heated to 70 ~ 90 ℃ and generates the dry product thionamic acid immediately to flaker by the second reactor continuous overflow, removes sulphur trioxide through de-gassing vessel again, the finished product thionamic acid content 93.58%, urea productive rate 94.67% relatively.
Embodiment 2
The continuous reaction apparatus that is composed in series by three reactors adds first reactor with the oleum of 161 part of 31% concentration per hour, 40 parts urea, stirs and cooling is controlled at 55 ~ 45 ℃ of temperature ranges; Again with per hour 35 parts of urea, 50 parts of sulphur trioxide (one section sulphur trioxide reforming gas of sulfuric acid plant, trioxygen-containing sulphur volume ratio 7.9%) speed adds second reactor, stir and cooling is controlled at 46 ~ 40 ℃ of temperature ranges, add its material temperature control of the 3rd reactor at 40 ~ 20 ℃ with the speed of 50 parts of sulphur trioxides (the same) per hour at last; The complex compound that reaction generates, is heated to 70 ~ 90 ℃ and generates the dry product thionamic acid immediately to flaker by the 3rd reactor continuous overflow, removes sulphur trioxide through de-gassing vessel again, the finished product thionamic acid content 93.00%, urea productive rate 93.56% relatively.
Embodiment 3
The continuous reaction apparatus that is composed in series by four reactors, with the oleum of 181 part of 22% concentration per hour, 30 parts of urea add first reactor, stirring and cooling control feed temperature are between 60 ~ 50 ℃, again with 30 parts of urea per hour, 35 parts of sulphur trioxide (one section sulphur trioxide reforming gas of sulfuric acid plant, trioxygen-containing sulphur volume ratio 7.9%) speed adds second reactor, again with 27 parts of urea per hour, 35 parts of sulphur trioxides (the same) add the 3rd reactor, the 4th reactor per hour adds 40 parts of sulphur trioxides (the same), the temperature of charge of these three reactors is controlled at 55 ~ 45 ℃ respectively, 45 ~ 40 ℃, 40 ~ 25 ℃, from first, second, the 3rd, the reaction mass that the 4th reactor overflows enters second respectively, the 3rd, the 4th reactor and flaker.The network and the thing that flow on the flaker are immediately heated to 70 ~ 90 ℃, and generate the dry product thionamic acid rapidly, remove sulphur trioxide through de-gassing vessel, the finished product thionamic acid content 93.45%, urea yield 95.02% relatively.
Claims (6)
1, a kind of preparation technology of two step method thionamic acid, wherein the first step reaction may further comprise the steps: continuously whole sulfuric acid or concentration are lower than first still that 38% oleum joins multi-stage reacting kettle, add urea and sulphur trioxide simultaneously, stir and cool off the formation reaction of inhibition thionamic acid, the wherein sulphur trioxide segmentation adding of limiting the quantity of, the first still sulphur trioxide cumulative amount is no more than and adds 75% of sulfuric acid mol number, sulfuric acid, three kinds of raw material accumulative total of urea and sulphur trioxide mol ratio is 1: 1: 1.3 ~ 1.6, each temperature of reaction kettle is set in 70 ~ 25 ℃ of scopes from high to low according to the sulphur trioxide additional proportion.
2, technology according to claim 1, described sulphur trioxide are the sulphur trioxide reforming gas of sulfuric acid plant.
3, technology according to claim 1, wherein said multi-stage reacting kettle, preferably 3 ~ 4 stills.
4, according to claim 1 or 3 described technologies, wherein said reactor adopts the mobile successive reaction mode of drop to operate.
5, according to claim 1 or 3 described technologies, when adopting the above operate continuously of 3 stills, the urea segmentation adds, but the final stage still does not add urea.
6, according to claim 1 or 3 described technologies, when adopting 3 still operate continuouslys, first, second and third still sulphur trioxide accumulative total add-on accounts for and adds 0 ~ 75%, 50 ~ 100%, 130 ~ 160% of sulfuric acid mol number, and first, second and third still temperature is controlled at respectively in 25 ~ 70 ℃, 25 ~ 55 ℃, 25 ~ 40 ℃ scopes.
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| CN 03159539 CN1272314C (en) | 2003-09-18 | 2003-09-18 | Two-step preparation technology of amino sulfonic acid |
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| CN 03159539 CN1272314C (en) | 2003-09-18 | 2003-09-18 | Two-step preparation technology of amino sulfonic acid |
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| CN1272314C CN1272314C (en) | 2006-08-30 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100361969C (en) * | 2006-07-07 | 2008-01-16 | 太原理工大学 | Method for synthesizing amino sulfonic acid series amphoteric surfactant |
| CN111302316A (en) * | 2020-03-05 | 2020-06-19 | 中国日用化学研究院有限公司 | Method and device for continuously preparing sulfamic acid |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023084314A1 (en) * | 2021-11-10 | 2023-05-19 | Shree Sulphurics Pvt. Ltd. | A process for the preparation of sulfamic acid |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100361969C (en) * | 2006-07-07 | 2008-01-16 | 太原理工大学 | Method for synthesizing amino sulfonic acid series amphoteric surfactant |
| CN111302316A (en) * | 2020-03-05 | 2020-06-19 | 中国日用化学研究院有限公司 | Method and device for continuously preparing sulfamic acid |
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| CN1272314C (en) | 2006-08-30 |
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