CN1321888C

CN1321888C - Method for manufacturing calcium borate from ulexite

Info

Publication number: CN1321888C
Application number: CNB2005100456528A
Authority: CN
Inventors: 胡德生; 丛锡岱
Original assignee: DASHIQIAO CITY BORON PRODUCTS FACTORY
Current assignee: DASHIQIAO CITY BORON PRODUCTS FACTORY
Priority date: 2005-01-10
Filing date: 2005-01-10
Publication date: 2007-06-20
Anticipated expiration: 2025-01-10
Also published as: CN1654327A

Abstract

The present invention provides a method for preparing calcium borate from ulexite. Powdered ore of ulexite is used as raw material, hydrochloric acid and lime are used as decomposing agents, and measured by the content of Na2O in ulexite, CaO and HCl required in decomposition reaction are added according to the mole ratio of Na2O: CaO: HCl=1:0.9 to 1.6:0.9 to 1.1. The mixture is stirred at temperature lower than 50 DEG C to react for 2 to 9 hours, and the pH is from 9 to 13. Products are filtered, washed and dried to obtain calcium borate products containing 39.0 to 42.5% of B2O3 and less than 0.5% of Na2O. Under the condition of not recycling concentrated solution, the one time boron yield is as high as 96 to 99.2%.

Description

Method with manufacturing calcium borate from ulexite

It is raw material with ulexite that technical field the present invention relates to a kind of, is the method that decomposition agent is made lime borate with hydrochloric acid and lime.

The background technology ulexite is important boron mineral resource, is the raw material of making borax and boric acid, also is applied in glass and the ceramic industry, because it contains a considerable amount of alkali metal (Na ₂O content is at 6-7.5%), limited its application in non-alkali glass.

Method by manufacturing calcium borate from ulexite also has some reports, for example:

1991, Colorabbia Italia S. P. A. was at Chinese patents 91104633.X, and the reaction principle of this technology is: 2[Na ₂O2CaO5B ₂O ₃16H ₂O]+NaOH → 2.5[Na ₂B ₄O ₇10H ₂O] ++ 4CaO5B ₂O ₃7H ₂O

Reaction conditions: temperature 120-200 ℃, pressure 2-16 crust, B ₂O ₃/ CaO=1-1.25, pH=11-12.This method is to be purpose to produce Sodium Tetraborate and lime borate, and the boron productive rate has only 50% in the lime borate product in theory.

This method shortcoming be 1. in the lime borate product productive rate of boron low; 2. reaction conditions is relatively harsher.

The shake Chinese patent technology 92110544.4 of imperial or royal seal application of thunders in 1992 is characterized in decomposing ulexite with carbonating ammoniacal liquor, and the calcium in the breeze is transformed into precipitation of calcium carbonate, and liquid phase is ammonium borate and dobell's solution.Lime carbonate and nonreactive impurity are removed in filtration, and the borate solution that contains ammonium, sodium is handled with nitrocalcite and aqua calcis, generates the nitrate and the solution of ammonium hydroxide of lime borate precipitation and sodium, ammonium.Through filtering separation, solid materials is drying again, promptly obtains the lime borate product, and filtrate is through evaporation concentration, and crystallisation by cooling is isolated solid nitric acid sodium, and mother liquor contains ammonium nitrate and sends back the manufacturing ca nitrate soln.

This method shortcoming is that production process is too complicated, investment and process cost height.

The objective of the invention is with a kind of production process simple and operational condition and decompose ulexite, and make boron wherein all change lime borate into than the demulcent method, and the productive rate height of lime borate.

Summary of the invention the present invention is with containing B ₂O ₃37-42%, granularity are that 60-200 purpose ulexite breeze is a raw material, are decomposition agent with hydrochloric acid and lime, press the Na in the ulexite ₂CaO in O, the lime and the hydrogenchloride mol ratio Na in the hydrochloric acid ₂O: CaO: HCl is 1: 0.9-1.6: 0.9-1.1 batching, stir down temperature of reaction＜50 ℃, pH=9-13 reacted 2-9 hour, reaction product after filtration, washing and dry, obtain containing B ₂O ₃39.0-42.5%, Na ₂The lime borate of O＜0.5%.

Contain NaCl 60-150g/L, B ₂O ₃The boron mother liquor of calcium of＜12g/L, pH=9-13, through evaporation concentration, isolate the NaCl solid after, contain B ₂O ₃But high concentrated solution Returning utilization.

Decomposition agent can also be hydrochloric acid and white lime Ca (OH) except that unslaked lime ₂Powder or milk of lime.

Know-why of the present invention is to be decomposition agent with hydrochloric acid and calcium oxide, decomposes ulexite by following reaction formula:

Na ₂O·2CaO·5B ₂O ₃·16H ₂O+2HCl+2Ca(OH) ₂→2CaO·B ₂O ₃·6H ₂O↓

+2CaO·3B ₂O ₃·9H ₂O↓+2NaCl

Calcium oxide as if adding surpasses in right amount, then also can further react to be:

Na ₂O·2CaO·5B ₂O ₃·16H ₂O+2HCl+3Ca(OH) ₂→5CaO·B ₂O ₃·6H ₂O↓+2NaCl

The production process of lime borate of the present invention is as follows:

Decomposition reaction: uncovered or have in the retort of band whipping appts of end socket, by liquid-solid ratio 2-8: 1 pack into except that lime slaking machine use all boron calcium washing lotions and part of boron mother liquor of calcium, press in the ulexite sodium oxide amount then according to Na ₂O: CaO: HCl=1: 0.9-1.6: 0.9-11 (mole) ratio.Under agitation condition, add ulexite breeze, lime and hydrochloric acid.Temperature of reaction＜50 ℃, reaction times 2-9 hour.The pH=9-13 of reaction regulates the calcium oxide content that adds and can obtain B ₂O ₃: the product of CaO=1: 0.8-1.1 (mol ratio).

Press filtration and washing: after decomposition reaction finished, to pressure filter, keep-uping pressure was the 0.3-0.6MPa filtration with the slip force feed in the retort.Filtrate flows in the boron mother liquor of calcium groove.After the filtrate filter is clean, with the clear water filter wash cake of 1.0-2.5 times of boron ore powder amount.Wash water flows in the boron calcium washing lotion groove, in order to returning batching and preparation milk of lime usefulness.After washing lotion stream is clean, with the moisture content in the pressurized air blowing filter cake of 0.3-0.6MPa.Till treating that dripless blows out.

Filtration cakes torrefaction: from the wet cake that pressure filter draws off, available Rotatingandflashstreamingdrier or hollow paddle stirring type dryer drying.Drying conditions is temperature of charge 120-180 ℃, and residence time of material is less than or equal to 3 hours, to the requirement of product and the pattern of used drying machine, adjusts drying conditions according to the user, can make to contain B ₂O ₃The lime borate product of 39.0-42.5%.

Mother liquor is handled: contain NaCl60-150g/L, B in the boron mother liquor of calcium ₂O ₃1-8g/L can separate the sodium-chlor of separating out down by evaporation concentration high temperature, and liquid returns boron calcium batching again; Perhaps use hydrochloric acid, pH=6-9 is adjusted in neutralization, discharges after conforming with environment-protecting industrial sewage drainage standard.

Description of drawings

Fig. 1 is the production process synoptic diagram with hydrochloric acid and lime decomposition agent and manufacturing calcium borate from ulexite:

Wherein: the 1-decomposition reaction; 2-filters and washing; The 3-product drying; The 4-mother liquor is handled.

A-hydrochloric acid, B-lime, C-ulexite breeze, D-lime borate product, the E-clear water,

The F-washing lotion, the G-mother liquor, H-makes milk of lime.

The present invention's characteristics of raphite preparing boric acid calcium method:

1, uses hydrochloric acid and lime, calcium hydroxide or milk of lime as distintegrant, decompose and contain B₂O ₃The raphite breeze of 37-42% is made line borate, and the product line borate of acquisition contains B₂O ₃41.0-41.5%, the yield of boron is up to 96-99.2%.

2, the decomposition reaction condition of this method relaxes, decomposition temperature＜50 ℃.

3, this method makes to contain NaCl 60-150g/L in the boron mother liquor of calcium owing to used hydrochloric acid, through concentrating isolated chlorination Sodium can be used as byproduct. Add hydrochloric acid and be neutralized to pH=6-9, can reach the environmental protection standard discharging.

Embodiment

Embodiment 1

In the retort that a uncovered band stirs, add boron calcium washing lotion 0.8m ³With boron mother liquor of calcium 2.2m ³Start stirrer, drop into ulexite and (contain B ₂O ₃38.7%, CaO 12.45% and Na ₂O 6.89%) breeze (granularity 90% is by 160 orders).After stirring, add hydrochloric acid 257kg that contains HCl 31.5% and the milk of lime 0.92m that contains CaO 160g/L ³Keep 32 ℃ of temperature of reaction, react to pH and reach 11; 6 hours time, i.e. stopped reaction.Material force feed in the retort to pressure filter, is kept filter pressure 0.4MPa, and filtrate flows into boron mother liquor of calcium groove.After treating that the filtrate filter is clean, use 1.8m ³Clear water is washed boron calcium filter cake, washing lotion flows into boron calcium washing lotion groove (prepare against preparing lime milk and return the use of retort batching).After drop to be washed is clean, blow down moisture content in the filter cake with 0.4MPa pressurized air, treat that water droplet blows off after, get final product discharging.Draw off wet filter cake 1670kg, filter cake is sent to the Rotatingandflashstreamingdrier drying, keeps 165 ℃ of drop temperatures, and (it contains B can to make the qualified product lime borate ₂O ₃41.5%, CaO 29.3% and Na ₂O 0.2%) 925kg, boron yield 99.2%.

The boron mother liquor of calcium contains NaCl 102g/L, B ₂O ₃2.45g/L, except that returning batching, remaining (1.27m ³) be sent to the sodium-chlor recovery process and handle.

Embodiment 2

In the retort that a uncovered band stirs, add whole boron calcium washing lotions and boron mother liquor of calcium 2.3m ³, start agitator, add and contain B ₂O ₃37.5%, CaO 12.1%, Na ₂O 6.68%, and granularity 90% is by 160 purpose ulexite breeze 1000kg.After stirring, add slaked lime 170kg that contains active CaO 71% and the hydrochloric acid 253.7kg that contains HCl 31%.35 ℃ of temperature of reaction.In 5 hours reaction times, pH reaches 9.8, finishes reaction.With retort slip force feed to the plate-and-frame filter press press filtration, pressure 0.4MPa, filtrate flows into boron mother liquor of calcium groove, treat that mother liquor all leaches after, use clear water 1.7m ³Wash boron calcium filter cake, washing lotion flows into boron calcium washing lotion groove, and after washing finished, the moisture content with in the 0.4MPa pressurized air blowing filter cake after waiting to blow off, can draw off filter cake, obtains wet cake weight: 1547kg.Wet cake is sent to drying process, with hollow paddle stirring type dryer drying, keeps 130 ℃ of dry materials temperature, 1.5 hours time.Dry back boron calcium product contains B ₂O ₃41.0%, CaO 28.15%, Na ₂O 0.19%.Weight 894kg, boron yield 97.74%.

The boron mother liquor of calcium contains B ₂O ₃100g/L, Na ₂O 6.5g/L, except that returning batching, remaining 1.26m ³Being sent to the sodium-chlor recovery process handles.

Claims

1, a kind of method of decomposing manufacturing calcium borate from ulexite with lime is characterized in that present method is with containing B ₂O ₃37-42.0%, granularity is that 60-200 purpose ulexite breeze is a raw material, is decomposition agent with hydrochloric acid and lime, presses Na in the ulexite ₂CaO in O, the lime and the hydrogenchloride mol ratio Na in the hydrochloric acid ₂O: CaO: HCl=1: (0.9-1.6): (0.9-1.1) batching, stir down temperature of reaction＜50 ℃, pH=9-13 reacted 2-9 hour, reaction product after filtration, washing and dry, obtain containing B ₂O ₃39.0-42.5%, Na ₂The lime borate of O＜0.5%; Contain NaCl60-150g/L, B ₂O ₃＜12g/L, the boron mother liquor of calcium of pH=9-13, through evaporation concentration, isolate the NaCl solid after, contain B ₂O ₃But the concentrated solution Returning utilization, the yield of boron reaches 96-99.2%.

2,, it is characterized in that with white lime or milk of lime replacing lime according to the preparation method of the described lime borate of claim 1.

3,, it is characterized in that dry lime borate filter cake is that the exsiccant condition is with Rotatingandflashstreamingdrier or hollow paddle stirring type dryer according to the manufacture method of the described lime borate of claim 1: the temperature 120-180 of dried material ℃, time of drying≤3 hour.