SK14596A3 - Method of producing methylen-urea and device for carrying out this method - Google Patents

Abstract

Disclosed is a production method by the reaction of methanal (HCOH) with urea (CO(NH2)2) in two reaction steps. In the first step of the production the liquid intermediate is prepared in the way, that in reaction medium 2 to 6 wt. parts of urea per wt. part of methanal, whilst the reaction mixture contains also 16 to 44 parts of water. Before the reaction, during it or immediately past, pH of the reaction mixture is modified to the value 4 to 12.5, whilst for the acidity of the reaction mixture modification is advantageous to use a carbonate and/ or alkali metal hydroxide, or oxide and/ or calcium and/ or magnesium hydroxide. In the second step of methylene urea production by the said method produced liquid intermediate is mixed with aciditively reacting substance, in consequence to which the course of the condensation reactions is catalysed. By the effects of exothermic reaction the reaction mixture is warmed to the temperature higher than 40 C, also the sequential change of its reological characteristics occurs and subsequently to complete extinction of the liquid phase from the reaction mixture. The reaction product is isolated from reaction medium in solid or slightly plastic state. It is suitable, if to the reaction product after its isolation from the reaction medium suitable alkali added. Disclosed is also device for performing of this method.

Description

The present invention relates to a process for the production of urea mytelenes and to a device for carrying out this process,

BACKGROUND OF THE INVENTION

In addition to conventional nitrogen sources such as nitrates, urea and various ammonium salts, a variety of organic nitrogen compounds are also used in their industrial process to ensure the gradual release of the nitrogen component. compound. Among these compounds, condensation products have a prominent role in the urinary tract. These erythromycin, which were developed in the 1930s and were initially used as thermosetting materials in the manufacture of plastics, In the second 1 c <i: i. c i š t. y r i d s i t y c h r o o v

D e p a r m t r i t o f A q r i <::: u 11 u r i z t i 1 i, that the products should also be taught as a source of gradual action: i. and c: s h o nitil ·: v are v i s; Viscous plants, but from a commercial point of view of researchers J n S.

n i e k t o · é é bi bi bi bi what is the most prod uct of the y and y: j o o o * o s p>:.! H r r s t r r o z S r r i. 1 ·:. ·. The urea with methanal - formaldehyde 'These are' grades of nitrogen-containing fertilizers since the early eighties. They are commonly known as UREAFORM and are produced by variously modified urine condensation reactions. methanalomine rtna 1 debiydom, whereby: :: iemo nokata 1 can be identified with: y 1 or bi ydroxides “ ) reak reak :: bi bi bi bi :: bi:

v z n i k p; r e d m e t h e r d o k t o v

About 'l

N'-TJ-C H _R CH

O '1

H ..... C - NH - C H = - NH - C - NH

-CH OH .....

Depending on the production method used, the products vary greatly in chain length, end groups, and it is understood that the properties of i i bi-agronomy: i. c. n n osť.

The first basic work related to quantitative assessment of the aforementioned measurements 1 KRALDVEC, R; D. and Morgan, W. A. J, Assoc. Offic. Agr. Chemists, 36, 907 (1953). J. Agr. Food Chem., 2, 92-1954).

These authors first introduced nitrogen fertilizers with gradual efficacy t. z v. the efficiency index, whose j) o d s t and t. n e n o n s all s d e? s i a t y c h r o o c h h e e) o d n o t. i 1 t: i. (J. Ftssoc. Offic. Agr. Chemists, 48, 1105, 1965).

It was found that d i met. In the soil, three urines (I) are mineralized too quickly (85% of the nitrogen is released within 4 weeks) and is therefore very weak, slowly acting fertilizer. The length can be used for fertilization within 26 weeks (WINSOR, GW-LONG, No. I. E, with J. Sci. Food Agr 9: 185 (1953). Tetramurea (II) appears to be the most suitable type of urea meth y for this purpose, but the synthesis of this compound has not yet been successful "

0 0 '1 H (|

HaN-C-NH-CH-α-NH-C-NH ... CH ₃ -NH-C-NH ₌ d: i. meth 1. en three urine per ^(T: '41 * /, N

0 ((j il l | H j

H and N-C-NH ..... CH. _and -NH-C-NH-CH _and -NH-C ... NH-CH-α-NH-C-NH _and trimethylenetetramycin (II)

0.6%

Production?. UREAFORM is disclosed in many patents and specialist publications. c. Most of them work with acid catalysis, usually differing only by the equipment used or by minor details. Examples of these works include:

ALMASSY, G, et al .. with Magy. Kem. Lap I, 28, 452 (1973); Hung.

Teljes 8, 158 (1974); H, 741 (1976);

BROADBENT, D. S .: Brit. 200 601 (1970); BRDWN, G. G .:

Brit. 1,348,181 (1974);

CREMER, J .: Chem. Ingr. Tech., 37, 705 (1965); Franc. pat. no. 1401-101 (1965);

"T

FRIDMAN, .S. D. - KLEVKE, V. A .: Žm. Ex. chim. 34, 2206 (1961); 38, 1091, 1965;

HAGI, N. COHEN, L .: Agron. J., 68, 518 (1976); Pat. USA, 3,336,128, 1964; Ger. Ofen č. 2,002,873 (1971); Ger. Offen č. 1,132,159 (1962); Ger. Offen No. 2,422,238 (1975); Cs. AO No .. 11.7 168 (1966) ·; Rol. pat..č. 52087 '

A1 k a 1 i a m i k a t. The processes used are less frequently reported in the literature and technologies using combinations of acidic and basic catalysis (LJSA pa. 3 759 687/1973) are also relatively rare.

F o r o c tio n o n t o r o n t, UREAFCR1, containing 42 * /. N, 17.7, cold water insoluble M and only 1 * A hot water insoluble N were patented by GRETDINGER, D. S. and COHEN, L. (U.S. Pat. No. 4,089,899). According to their solution, the urea in the form of its 20-40¾ aqueous solution is reacted with formaldehyde, with the molar ratio of COíHHs) · HCOH = 3- · 2 s 2-1 2-1 and the pH of the reaction mixture is adjusted by addition of dilute alkaline hydroxide. pH: 8.5. The reaction mixture is then acidified. to a pH of 3.8 and the condensation is carried out at a temperature of 20 to 40 ° C for about 3 hours. Finally, the reaction mixture which has an alkali hydroxide (pH 3.5) is added to the reaction mixture. The reaction product - UREAFORM is a 1 to 5, 11, 8, 9, 10, 10, 10, 10, 10, 10, 10, 10-day cake and dried, usually 3-5 parts by weight of dry product being obtained. parts -filtrate.

Although this method provides a quality product, its use for mass production is not very efficient, time and energy consuming, it requires. per unit amount of finite 1 non-productive volume capacitiesproducting, productoreproducts and meanders from a relatively demanding filtration and it is also necessary to count with its drying, while the production process is the source of the unpleasant hoazekoogical aspect and S ko

1 Disposable filtrates containing residual formaldehyde methanal, which can only be partially recycled in the manufacturing process.

SUMMARY OF THE INVENTION

Disadvantages which prevent and extend the hitherto known methods of production of methylene urea under conditions. Mass production is largely solved by technology within the meaning of the present invention. Advantage. of the method of manufacturing according to the invention is in particular:

methylene urea exits directly from the process in the solid state - without the need to isolate it from the reaction mixture by filtration, and. n e h a n d e c h e n e n e n e n e n e n e n e n e n e n 11

- no liquid waste is produced during the production process,

- where appropriate, the manufacturing process; can be divided into two processes, which can be separated by local and temporal preparation of the liquid intermediate and the actual preparation of met. y l n o o n i n y,

- the production method is simple and easy to operate, the technology has minimum energy consumption requirements,

- the use of vanor. ' In the case of superphosphates and production, it is possible on a production plant that is less expensive to manufacture and that it is less expensive to manufacture.

Method of production of urinary urea by reaction of urea (00'NH _and 5 - ,;) cream 1 om - form 1 (Ehedi HC o H) under 1 degree cut, different, which may be in place and also in the process, and also with urea prepares reactions, s; and liquid, s consists of two bases also realized separately - at different times.

In the first stage of the reaction, the reaction of methane 1 involves a solution solution limit. product. U is F rocedure is thereby such that the reaction medium is accounted for by a mass portion metanalu (HCOH) 2-6 .diel mass of urea (CO _{(NH,) Å).} In order to prepare methylene urea, the nitrogen of which can be used for a period of 2 to 5 months, it is suitable that, for 1 hand, a portion of HCOH in the reaction mixture accounts for 3.2 to 4.4 masses. parts of urea. In order to ensure the advantageous properties of the liquid intermediate, and in particular to avoid the liquid phase content of the final product, it is necessary to ensure that the reaction mixture contains at least 16 and at most 44 masses. Λ water, preferably at least 23.2 and at most 29.7% by weight. % water. In order to ensure that the reaction grain is preloaded, it is advisable to use urea in solid form and metanal-formaldehyde in the form of its highly concentrated aqueous range (so-called formalin) - it is appropriate to use 30 to 42% formalin. . it usually contains a certain amount of acid-reacting substances (eg formic acid, HCOOH), which causes aqueous solutions of methanal often to react significantly acid (pH 2). I '. For these reasons it is advisable to at least partially adjust its acidity of the alkali before the reaction with urea. The essence of the liquid intermediate in the first stage of production is primarily mono- and polymethylol urea, while in order to of the mixture before, although in the course of, and 1 ebopo r-eactioninet of 1 µs with urea, to a value of 4.0 to: 1.2.3. from an alkaline addition of metal (potash, oxide and / or.

is preferred

NaOH and the like) or calcium. (s), soda, KOH, magnesium hydroxide. . .

In the second reaction step, the liquid intermediate, containing mainly urea mono- and polymethylol, is mixed with an acid-reacting substance, whereby the course of the acid-catalyzed polycondensation is directly initiated. Particularly suitable acid-reactive, material for this purpose has proved to be orthophosphoric acid (H®P0 ^), or a mixture of dipotassium hydrogen with one (ΚΗ Ρ0 ₌ ^, ΝΗ. ,,. Ι- Ι · · ₌ Ρ0.ι ,. , Ca (H 2 PO 4, and the like). Due ykondenzačne.j half of the reaction, the reaction mixture was ^Zoe: irejenatep otuvy 1 N N i. than the product is eothermically hoteplexed: i. e), a mixture of a rheological reaction, a post-product of the reaction medium in a solid or only to stop polycondensation of methylene urea, it is appropriate to add a suitable alkali. As it turned out to be one of the carbonates

C (further reacting and resulting in a liquid phase from the reaction further isolates from the reaction a slightly plastic state. In the stabilization of the product to a solid reaction product suitable for this purpose alkali metal (potash, soda and etc.) and / or calcium and / or magnesium hydroxide and / or magnesium hydroxide (e.g., calcium hydrate powdered slaked building lime, up to 1: i. pnoapod), but it is also possible to use gaseous ammonia or a gas in it, up to 1 omit 1 et

The apparatus for carrying out the process according to the invention consists of at least one _; from the stirred reactor 7. s. ep 1 a) (duplicator, heating circuit, integrated heat exchanger, etc.), A liquid intermediate is prepared in a stirred reactor. reaction of urea (A) with met. The alkali (E), wherein in order to adjust the pH of the reaction mixture also alkali (C) ..... potash, soda, KOH, NaOH and the like are fed into the reactor.

In order to ensure the continuous processing of the prepared liquid intermediate (D), it is preferable to feed the feed. The liquid intermediate (D), consisting predominantly of mono-polymethiol urea, is metered by the feed system 2 into a continuously operating mixer 4, into which also the acid-reactive substance 4) is metered by the feed system 3.

The continuously operating mixer 4 is suitable to be solved as a mixer. d o m 1 o n t. c o m e :: h o c b m e n i n e, 6 and 1 n o t i n t o n t o n t o n o n t o n t o n t o n t o m e t. y 1 é n m o v i n y ρ o d o n e n e s 1 1.1 e n e s. R e t e n d e n x e 5. in m e sad1om, and j. e b o

DC: i.

I!

or a continuous state of operation, whereby the reaction mixture changes substantially from the free-flowing liquid to the liquid phase. The disintegration of the reaction product is provided by an apparatus 6, the design of which depends on the design of the apparatus 5. The crushing device 6 is expediently designed to simultaneously homogenize the product with the alkali (F) which is fed into this part of the production process by means of an alkali dispenser 7. In order to dry the product, especially at a higher water content of the liquid product to be treated? alternatively, it is possible to include in the assembly a device 8 for drying the reaction product »

Furthermore, it has been found that some of the batches may be advantageously used to produce the methylene urea of the invention. m i k o t i n n a 1 e b o k o t i n n a p e 'a c u i i c h z a riade? used for the production of superphosphates by the decomposition of phosphates and the like. t. 1. In the case of semi-continuously operating types of equipment, the so-called equipment can be used for production purposes. ventricular superphosphate production (eg STLJRTEVANT.ov. process, '' including chambers, type SVENSKA and 'KILCH, OBERPHOS process', etc.).

For the continuous guided process for the production of methylene urea according to the invention, one of the systems for solidifying the reaction mixture on a moving belt (e.g. BROADFIELD, NORDEN3REN, KIJHLMANN, etc.) in a rotating drum (e.g. MONTECATINI, 5AINT- G0BAIN, STURTEVANT PD process, etc.), or in a rotating chamber according to the ver-1 axis. Z o z and r: i. a d e n :( t o o t o o s 1, and in the countries of the former Soviet influence, the modified t echo of the MOR ITZ-STANDAERT type was extended.

Of the facilities used for the production of superphosphates, it is possible to use only. the part of the apparatus in which the state of the reaction mixture changes from liquid to solid, impact 5 and / or the apparatus used to recover fresh reaction product A.

Examples

The solutions according to the invention illustrate, illustrate and illustrate the invention and all of the above-mentioned examples.

Example 1

The flasks placed in a water tempering bath and equipped with a double-wing stirrer were provided with 610 ° C s e c tio n s, having a content of 3. 41 hours. X

HCOH - In order to treat the acidic reaction of methanol, 11.6 g of ammonia water containing 25 wt. X NH®. Thereafter, 373.4 g of urea fed were fed while heating the bath to about 50 ° C and stirring continuously. The urea was dissolved in about 30 minutes, to a liquid intermediate containing 27.2 wt. X nitrogen and

24.6 X water. The prepared intermediate was worked up into a mixture of 1 to 10%. * 1 1 p o o o o 1,,,........ e n i n e d e n e e n e n e e n i e n i d e s e n i e n e n e n e n e n e n e n d e s.

Example 2

220.8 g of an aqueous solution of methaha-formaldehyde (36-387 HCOH / d 1.08 g.cm ^-3 ) was not weighed into a beaker placed in a water tempering bath. This was preheated to 41 [deg.] C. and 279.2 g of the added urea &quot; additive &quot; from 1 to 24 &apos; Next, 9 g of about 407 KOH solution was added to the reaction mixture. The dissolution of the urea residue took about 10 and 15 minutes while stirring with a double-blade stirrer at a reaction temperature of 28-37 ° C. After the dissolution of the whole cynomolgus: i. 5. For the purpose of adjusting the pH to 11.1, 0.8 g of an aqueous solution of KOH were added.

On the second day, the liquid acid intermediate catalyzed by polycondensation was converted to another product, urea methylene urea, to 509.8. g of the liquid intermediate is stirred with efficient stirring. In addition, the reaction mixture gradually thickened and later became a white viscous cream until it finally solidified, in order to dull the acidity of the reaction product. o 21.8 gc: ca 4 0 7 solution K 0 H.

Example 3

To 232.2 g of forinaline (36-387 HCOH; dist. 1.07-1.09)

g. cm - *), foreplay: i. in the water bath. ' and 40 ° C, 417.8 g of flax urea was added with stirring as a result of which the temperature of the reaction mixture dropped to 21 ° C.

Dissolution of 10 g of flaky KOH in 40 g of distilled water resulted in a 207 KOH solution used in the next step to gradually adjust the pH of the reaction mixture.

After stirring for 221 minutes, the entire amount of urea was practically dissolved (pH: 4.09) and the pH of the reaction mixture was gradually adjusted. Prior to the first addition of the KOH solution to the reaction mixture, a shelf-life sample was taken. Next, an aqueous solution was gradually added

K O H, in which the weight of the fish is about 1 to about 3 to about 3 ° C with alkali, logs. I. pH changes of the reaction mixture were monitored and a sample of the reaction product was always taken to test its shelf life. The obtained data are summarized in the following overview of the game.

Reaction Temperature Addition of K0H Flow -------------------------------------- --------

time C m i n 3 C ”C3 Cg 20 ´ /, KOH / 1 g R ¾ 3 before addition a p o Alkali KOH 48 0 4.07 - 27 44.5 0.7 4.07 8.5 35 40.5 1.4 8.44 7.5 40 40 2.8 7.48 10.5 After collection last - v order of the fourth sample -  holi ohrev reacting mixtures and so on mixing it interrupted " By measuring

determined that the undiluted sample of the liquid intermediate had an alkaline reaction (pHt 10, S) and its measured mass at 20 '= 8 bare equal to 1.727 kg.m ^-55 .

The samples taken, differing in the content of the alkali added and thus in the pH, were monitored for their traceability. even at room temperature (approx. 20 ^e C).

Sample without addition of alkali (pH 4.07) spontaneous by day; condensation - the next day it had the character of a thick suspension.

The first batch (pH; 10.5) after one day storage contained about 1/4 volume of crystals at the bottom of the vessel.

The sample with the lowest real addition of alkali (pH &gt; 8.5) showed the highest stability. The crystalline fraction deposited in the investigated samples was dissolved by heating to 30-40 = · 8, whereby the sample of the liquid intermediate regained the character of a clear, colorless solution.

Example 4

Into a sulfonation flask equipped with a stirrer and a thermometer, placed in a water tempering bath, was weighed 556.5 g of formine containing 37 g of I-CO 2. in 100 ml. The aqueous methanol solution used further contained 1% CH ₃ OH, to 1% Melamine and 0.016% HCCCH (formic). The density of the material is equal to 1110.3 kgm ^"3 at 18 ^e C and pHs 1.41.

To the methanal charge was added 8.23.7 g of urea added. Fo. 24 m · Inut stirring and temperature control was achieved the reaction 'of that p1 ol 4 0' ^and C, the ommo No No ovinabo 1 and at f n, and praktickyrozpuste. After 30 minutes, the reaction mixture reached 50 ° C while increasing the temperature at 1 ° C for 1 second and then increasing to 60 ° C for a further 2 minutes (pHs 3.24 ·). At this temperature, the reaction mixture was stirred at room temperature for 1 h. gave 4..5 g of powdered technical potash (approx. 85 * /, K _and 80 ~ _s ) and holo shut down the system with a water bath (40-45 ”8). After stirring for 35 minutes, the reaction mixture was a completely clear viscous solution (pH: 10.6). Prepared liquid honey ziprs: 1, characterized as follows:

specific gravity - density d _Λ 1244.3 kg., m ^{5 5} dry matter content (constant weight by drying at 105 ° C 63.5 ° C) storage at room temperature (18 20 ° C):.

at least 5 days *. ''

Liquid honey product. in the sense of the invention, it was further used for acid-catalyzed polycondertation tests on methylene urea. It has an acidification of the liquid intermediate product. dihydrogenphosphoric acid containing 75.5% H ₃ PO ₃ , i.e. 54.7 F (di = 1.5644 g.cm ³ ). During the laboratory tests of this series, 0.7 g to 7.05 g of the specified acid (0.38-3.6% in the reaction mixture) was added per 100 g of the intermediate liquid, while monitoring the rheological and temperature changes in the system with stirring. In the course of several repetitions of the tests with the different acid addition carried out. confirmed that the condensation reaction rate was half; directly proportional to the quantity of acid addition. In terms of flow rates, the creamy nature of the reaction mixture was observed within 480 seconds (0.38% ΡχΌ-), respectively. 12 seconds (3.60% Ρ ^ Ο ») a. similarly, the maximum reaction temperature was 48 ° C (0.38% Ps 0 0), respectively. 63 ° C (3.60% Pi? 0 _c .). The prepared samples were solid, of fresh slightly plastic character.

Example 5

C ontin 1 selects the vine c anthers, for the production of Special Combined Fertilizers of the type: 20--5--8--2 MgO, designated hanakva 1. ific ivu L f- v v as as as,,,,,,,,, sp bo, bo bo,, bo bo. bo. d e n u u u u n u m '. v p r d c t a d d a. Welding triple super phosphate - This was a modified N0RITZ - 8TANDAERT type device with a chamber rotating about a vertical axis, a sintered tin p Sloping belt, inclined into the rotary spreader. To homogenize the reaction mixture. used a premixing system in a built-in static mixer and subsequent mixing in the mixer, but not in the mixer. e S and i.

First Stage of Production - W orking in P a rd ed ed: i. product was. in a stirred reactor of a volume of 10 m &lt; ^{-5 &gt};, equipped with an efficient stirrer and steam heating by means of a duplicator. In principle, the preparation was similar to Example 5.

The prepared liquid intermediate was collected in a railway tank,. by which it was transported for further processing to the super f os farm. Extraction trihydrogenphosphoric acid containing 52.5 V total P 4 D-3 was used as catalyst acid component during production. Both liquid reactants were transported to a two-stage system of homogenization by centrifugal pumps, through a dosing system based on which the induction flowmeters were incorporated into the pipeline routes prior to their discharge into a static mixer.

An average of 41.400 kg (33.390 liters) of the liquid intermediate and 1080 kg (655 liters) of phosphoric acid extraction was metered into the mixer per hour. The mixture of dosing components premixed in the built-in static mixer was further homogenized in a rapid mixer from which the reaction mixture of the thin white cream type flowed slowly into the progressive mixture. The temperature of the reaction mixture in the chamber ranged from 65 to 75 ° C. The solid reaction product was successively cut into an inclined belt by means of a milling cutter forming part of the chamber, by means of which it was gradually conveyed to the rotating chamber to solidify the reaction rotary spreader. The surface of the material on the belt is p. The process is carried out for 1 hour of 1220 hours of technical powdered potassium carbonate (85%).

To convert the solid chill, the draining of the solid, freshly carved product, the urea methylene, is carried out. its ro sweeping transp. orusk 1 adovacejha 1 y centrifugal spreader. In this way, an hour is produced in excess of 30 tsu shyme. The product contained an average of 38.2% by weight. % N, 1.9 wt. * / P ₂ ( _{s s} and 2.6 wt.% Kat) in dry matter.

Claims (3)

PATENT N O R O K, Y A method for producing a urea drug by reacting methanal with urea in the presence of urea. The first step is that both are reactive. onmet an a 1 is a liquid preparation, preferably a ruptured intermediate, in the reaction. environment and the haptic portion metanalu (HCOH) optionally up to 2 parts of urea 6'hmotových <COíNH _{p) =),} preferably 3.2 to 4.4 parts by hmotovýoh urea, wherein the mixture comprises at least 16 amaim s no 4 1 4 weight C hpercent water, preferably at least 23.2% and maximum 29.7% by weight of water, the pH of the reaction mixture is adjusted to between 4 and 1.2.5 before, during or after the reaction, preferably by adding carbonate and / or or an alkali metal hydroxide or the addition of calcium and / or magnesium oxide and / or hydroxide, wherein in a further step; tupn: i. is said msp prepared by drip 1 = m? The dzi product is admixed with an acid-reactive substance, preferably a silicone. hydrogen phosphate, since the fire-reaction mixture is heated to a temperature of more than 40 ° C by the reaction heat released and the rheological properties gradually change and subsequently disappear even in the liquid phase of the reaction mixture, the reaction product further isolating the reaction medium in a solid or only slightly plastic state, where appropriate and optionally a suitable alkali may be added to the reaction product. and / or oxide and / or hydrated foam and / or magnesium oxide 2. An apparatus for carrying out the production method according to item 1, comprising at least one stirred reactor 7; by supplying heat from the outside for the preparation of the liquid intermediate by reacting the methanol with urea to the feed system of the liquid homo intermediate 2, the system (which gives the forging of the acid 1), the reactant 3, the contaminant. A non-working mixer 4 serving to homogenize the liquid limit: the product with the acid-reacting substance, batch-wise or continuously operating apparatus 5, in which the state of the reaction mixture from the liquid to the solid phase is changed, of the apparatus 6 intended to disintegrate the fresh reaction product and optionally also for its homogenization with the alkali dosed by the apparatus 7 and optionally also from the apparatus □ <4 with 1 s. 3. Equipment for. carrying out the production method according to claim 1, which has all the features of point (Ξ), characterized in that the apparatus used for the production of superphosphates or at least some of its parts, preferably the part of the apparatus in which the altering the solid state of the reaction mixture to a liquid phase; and / or a device for comminuting the fresh reaction product 6.