CN1049203C

CN1049203C - Solid composite containing sulfuric acid and its application

Info

Publication number: CN1049203C
Application number: CN94111761A
Authority: CN
Inventors: 陈天朗; 肖慎修
Original assignee: Sichuan Union University
Current assignee: Sichuan Union University
Priority date: 1994-05-24
Filing date: 1994-05-24
Publication date: 2000-02-09
Anticipated expiration: 2014-05-24
Also published as: CN1113934A

Abstract

The present invention provides a solid composite product containing sulfuric acid and a production method thereof. The solid composite product containing sulfuric acid is made from sulfuric acid solution, urea and certain additives. The solid composite product containing sulfuric acid, which is obtained by the method, has the advantages of convenient storage, transportation and use. The solid composite product containing sulfuric acid can be widely applied to the fields of chemical fertilizer preparation, soil improvement, chemical cleaning, etc.

Description

A kind of vitriolated solids composition and application thereof

The present invention is a kind of vitriolated solids composition, belongs to the inorganic chemical product production field.

As everyone knows, sulfuric acid particularly has a wide range of applications in Chemical Manufacture in all trades and professions, and only in chemical fertilizer (particularly phosphate fertilizer) was produced, the annual consumption of China just reached nearly ten million ton.Owing to sulfuric acid is the acidic liquid of deep-etching, in storage, transportation and use, very big inconvenience is arranged all, therefore,, be undoubtedly a thing highly significant if can there be a kind of method can obtain solidifying sulfuric acid easily.

At present, also there is not a kind of curing sulfuric acid product that can provide and have broad practice to be worth in a large number in the world.Hydrazonium sulfate is a kind of sulfuric acid of white crystal shape and the adducts of hydrazine, sulfuric acid wherein can discharge in the aqueous solution, thereby can regard a kind of curing sulfuric acid as, but because it costs an arm and a leg and the reductibility of hydrazine itself and do not have widespread usage and be worth, other more similar organism and vitriolic adducts also have kindred circumstances.In addition, also have a kind ofly to add silicate in the sulfuric acid and make its solidified gel sulfuric acid, but it is not a kind of curing sulfuric acid of real meaning, but a kind of strong thixotropic sulfuric acid colloid of having of silicate that contains.

In fact, with urea and sulfuric acid reaction be can generate 1: 1 or 2: 1 solid adduct (referring to L.H.Dalman, J.A.C.S., 56,549, (1934)), their water solubles, and sulfuric acid is discharged, but owing in this process of product development serious surfusion is arranged, thereby be difficult to crystallization, or can not get solid phase prod sometimes at all, or be cooled to certain temperature sometimes and just crystallize into a bulk ofly suddenly, be difficult to from reaction vessel, take out, be difficult to carry out (referring to United States Patent (USP) thereby make to produce, NO.4397675 (1983), NO.4447253 (1984)), therefore, external also have only urea and sulfuric acid processing generated the very strong fluid of a kind of viscosity or semi-fluid sell as liquid fertilizer (nitrogenous 9～27%, sulphur 9～25%).We are repeatedly also running into above-mentioned situation in the experiment.For example in experimentation, 1.2Kg urea slowly added 1Kg concentration and be in 98% the sulfuric acid and reacted about 30 minutes, this moment, temperature of reaction maintained the temperature in 90～120 ℃ of scopes with cold water exterior cooling in reaction vessel, temperature of charge is slowly descended, there is no crystallization to 70 ℃ separates out, also lose crystallization up to 30 ℃, even be cooled to 24 ℃ and also lose crystallization and separate out, but it is a bulk of to stir just crystallization suddenly a little, be difficult to take out from container, therefore thisly only be not suitable for scale operation with the way of urea and sulfuric acid reaction formation solidification sulfuric acid (to call curing sulfuric acid in the following text).Also there is the people this to be done effort abroad, tries every possible means to be improved, but also do not see what effect there be (seeing United States Patent (USP), NO.4447253 (1984)).

Purpose of the present invention will propose a kind of preparation crystalloid exactly and solidify the sulfuric acid composite scheme, enables to be suitable in scale operation, to obtain a kind of curing sulfuric acid fast, and its application of extensive exploitation, be social create beneficial result.

Technical scheme of the present invention is: (1), it with 15～30 weight part urea and 24.5～32 weight part concentration 70～98% sulfuric acid reaction, temperature remains in 90～120 ℃ of scopes, some additive that adds urea and sulfuric acid gross weight 0.5～5% weight part simultaneously in reaction or in process of cooling is formed the curing sulfuric acid composite, so just can obtain the crystalline powder shape and solidify the sulfuric acid composite product, wherein acid content is to be 45～62%, and said additive can be a zeolite, terra alba, water glass, rhombspar, kaolin, attapulgite, wilkinite, sepiolite, diatomite, the sulfuric acid of ammonium and sodium or phosphatic one or more add simultaneously; (2), will solidify sulfuric acid composite as the phosphorus decomposing agent, press " dry method " mixing at normal temperatures and pressures of 1～3: 1 weight ratio maybe when solidifying acid mode granulating to spray or to spray when uncured with the ground phosphate rock of different grades, use ground phosphate rock just can obtain to contain 12～17% nitrogen again, contain 6～15% P with " semidrying " parcel ₂O ₅The nitrogen phosphorus of (relevant with ore grade) is multiple fertile, and wherein the phosphorus decomposing rate of phosphorus is different and different with the ratio of ground phosphate rock with used curing acid in the ground phosphate rock, can optionally regulate, and reaches as high as more than 90%; If will improve the also available curing nitric acid of the nitrogen content N in the product ₂H ₄COHNO ₃(seeing Chinese patent, number of patent application 87103006 (1987)) instead of part solidifies sulfuric acid composite; (3), with solidifying the properties-correcting agent that sulfuric acid composite also will can be used as fused(calcium magnesium)phosphate or other thermal process phosphatic fertilizer, make the molten phosphorus of Chinese holly in them partly become water-soluble phosphorus.Polynary multiple fertile as making, also can when mixing, be added in and contain K in the finished product ₂O is not less than 4～6% KCl or K ₂SO ₄And 0.1～2% the required micronutrient element soluble inorganic salt of each kind of plant; (4), sulfuric acid composite be will solidify and directly or in preparation the solvable living micronutrient element inorganic salts that solidifies sulfuric acid composite gross weight 0.1～3% weight part, 0.5～5% weight part NaH added simultaneously ₂PO ₄Or monoammonium phosphate or two ammoniums, 0.1～8% weight part Na ₂SiO ₃, just can be with it as soil improvement agent (regulate soil acidity or the invalid phosphorus in the soil is activated); (5), will solidify sulfuric acid composite directly or in its preparation process, add the Sodium dodecylbenzene sulfonate or the sodium alkyl sulfate of sulfuric acid composite gross weight 0.1～2% weight part again, can be used for the cleaning of glass, enamel and metalware or some industrial equipments etc. used as chemical.

As mentioned above, utilize composition of the present invention, can make sulphuric acid soln become the curing sulfuric acid of crystalline powder shape, be convenient to store and transportation, can satisfy the special applications of some aspect, thereby bring very great change for some industrial production, for example above-mentionedly use it for phosphate fertilizer industry, can be implemented in normal temperature and pressure and make the multiple fertilizer of nitrogen phosphorus from ground phosphate rock through time processing with " dry method " or " semidrying ", thereby produced a kind of phosphate fertilizer new process for processing, save energy and investment reduce or eliminate environmental pollution in a large number, and low-gradely in can utilizing (contain P ₂O ₅〉=10%, but be good) the direct composting of phosphorus ore (powder) with 〉=15%; Other thermal process phosphatic fertilizers " dry method " such as all right fused(calcium magnesium)phosphate, defluorinated phosphate mix, and carry out modification, improve its quality; In addition this composition is used to do soil improvement agent, can regulates the PH of soil, and can make the invalid phosphorus activation in the soil be available phosphorus, can not execute or Shaoshi phosphate fertilizer; Said composition is used as chemical, can use little to family, greatly to the cleaning of the various dirts of mechanicals (incrustation scale, just dirt, grease, rust staining etc.), owing to urea itself has corrosion inhibition, so can use no or little inhibiter, thereby can reduce cost, reduce expenses.

Under constantly stirring, adding fills in the 5.0Kg98% vitriolic aluminium vessel embodiment one with 3.2Kg urea, notes making temperature of reaction be no more than 120 ℃ with cold water.Question response is back (about 20 minutes) fully, places and is cooled to 80 ℃, stirs the zeolite that adds 0.0164Kg, continues cooling, can get crystalline powder shape sulfur acid solids composition 40 ℃ of stirrings;

Embodiment two methods are got 4.5Kg urea and are added 5.0Kg75%H with embodiment one ₂SO ₄In, reaction back adds 0.18Kg water glass, is cooled to 35 ℃, has crystalline solid to separate out, and filters it, get final product vitriolated solids composition;

It is 45% curing sulfuric acid composite 0.1Kg that embodiment three gets acid content, adds 0.1Kg and contains P ₂O ₅27% ground phosphate rock, " dry method " mixes it, and it is multiple fertile promptly to make nitrogen phosphorus, wherein nitrogenous 12.5%, contains P ₂O ₅9.8%, its phosphorus decomposing rate is 73%, and this fertilizer is used for wheat, corn, paddy rice do farming examination, and they are suitable with other compound manure fertilizer efficiency that waits nitrogen phosphorus.For example test with wheat the academy of agricultural sciences in Sichuan Province, is waiting under the nutrient situation, and the output that general calcium adds nitrogen is 425.3 kilograms for every mu, and be 426.8 kilograms for every mu with the fertilizer output that this law makes;

Embodiment four except that composition and mineral powder, adds 0.02KgKCl with embodiment three again, dry mixed it, then must contain 11.4% N, 9.0% P ₂O ₅, 5.4% K ₂The ternary of O is multiple fertile, and the sub-district corn test of academy of agricultural sciences, Sichuan shows, wait under the nutrient situation multiple quite fertile with other.As the multiple fertile output that makes with general calcium is 40.34 kilograms, and the multiple fertile output that makes with fused(calcium magnesium)phosphate is 39.25 kilograms, and the multiple fertile output of ternary that makes by this law is 41.29 kilograms;

Embodiment five adds sulfur acid solids composition 0.015Kg in the 0.1Kg fused(calcium magnesium)phosphate, " dry method " mixed, promptly become a kind of modified calcium magnesium-phosphorus fertilizer, makes about 2% citric acid soluble phosphorus become water-soluble phosphorus, owing to contain nitrogen in the composition, cause this modified calcium magnesium-phosphorus fertilizer to become a kind of compound nitrogen phosphate fertilizer;

Embodiment six usefulness solid sulphuric acid composition 0.5Kg add composition weight 0.025Kg, Zn (NO again ₃) ₂, 0.005KgFe (NO ₃) ₃9H ₂O, 0.005Kg NaH ₂PO ₄, 0.025Kg Na ₂SiO ₃, add in the soil of 0.2Kg PH=8, thorough mixing, this P in soil H becomes about 6.9;

Embodiment seven gets and solidifies sulfuric acid composite 0.05Kg (having added the 0.0001Kg Sodium dodecylbenzene sulfonate during preparation), puts into the urinal of serious urine dirt, soaks 5 minutes with the little water dissolving, and water washes away then, and just dirt is removed immediately.

Claims

1. vitriolated solids composition, it is characterized in that said composition is the crystalline powder material, it is to be to form with the additive combination that accounts for sulfuric acid and urea gross weight 0.5-5% behind the sulfuric acid reaction of 70-98% by 15-30 weight part urea and 24.5-32 weight part concentration again, and said additive is selected from one or more the mixture in zeolite, gypsum, water glass, wilkinite, the diatomite.

2. the composition of claim 1 is as the purposes of the phosphorus decomposing agent of ground phosphate rock.

In the claim 1 composition as the purposes of fused(calcium magnesium)phosphate and other thermal process phosphatic fertilizer properties-correcting agent.

In the claim 1 composition as the purposes of soil improvement agent.

In the claim 1 composition as glass, enamel, metalware and Industrial Boiler, the purposes of the scale remover of dirt in the radiator.