CN1188747A - Method for producing gypsum series product using citric acid industrial waste residue - Google Patents

Method for producing gypsum series product using citric acid industrial waste residue Download PDF

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Publication number
CN1188747A
CN1188747A CN 97105654 CN97105654A CN1188747A CN 1188747 A CN1188747 A CN 1188747A CN 97105654 CN97105654 CN 97105654 CN 97105654 A CN97105654 A CN 97105654A CN 1188747 A CN1188747 A CN 1188747A
Authority
CN
China
Prior art keywords
citric acid
mentioned
waste residue
plaster stone
industrial waste
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN 97105654
Other languages
Chinese (zh)
Inventor
郭德光
孙永奇
李伯华
陈伟
王桂兰
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rizhao New-Type Building Materials Co Ltd Shandong
Original Assignee
Rizhao New-Type Building Materials Co Ltd Shandong
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Rizhao New-Type Building Materials Co Ltd Shandong filed Critical Rizhao New-Type Building Materials Co Ltd Shandong
Priority to CN 97105654 priority Critical patent/CN1188747A/en
Publication of CN1188747A publication Critical patent/CN1188747A/en
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B11/00—Calcium sulfate cements
    • C04B11/02—Methods and apparatus for dehydrating gypsum
    • C04B11/028—Devices therefor characterised by the type of calcining devices used therefor or by the type of hemihydrate obtained
    • C04B11/036—Devices therefor characterised by the type of calcining devices used therefor or by the type of hemihydrate obtained for the dry process, e.g. dehydrating in a fluidised bed or in a rotary kiln, i.e. to obtain beta-hemihydrate
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B11/00—Calcium sulfate cements
    • C04B11/02—Methods and apparatus for dehydrating gypsum
    • C04B11/024—Ingredients added before, or during, the calcining process, e.g. calcination modifiers
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B11/00—Calcium sulfate cements
    • C04B11/02—Methods and apparatus for dehydrating gypsum
    • C04B11/028—Devices therefor characterised by the type of calcining devices used therefor or by the type of hemihydrate obtained
    • C04B11/032—Devices therefor characterised by the type of calcining devices used therefor or by the type of hemihydrate obtained for the wet process, e.g. dehydrating in solution or under saturated vapour conditions, i.e. to obtain alpha-hemihydrate
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B11/00—Calcium sulfate cements
    • C04B11/26—Calcium sulfate cements strating from chemical gypsum; starting from phosphogypsum or from waste, e.g. purification products of smoke
    • C04B11/262—Calcium sulfate cements strating from chemical gypsum; starting from phosphogypsum or from waste, e.g. purification products of smoke waste gypsum other than phosphogypsum
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
    • C04B22/08—Acids or salts thereof
    • C04B22/14—Acids or salts thereof containing sulfur in the anion, e.g. sulfides
    • C04B22/142—Sulfates
    • C04B22/143—Calcium-sulfate
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/20—Retarders
    • C04B2103/22—Set retarders

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

A process for producing series of gypsum products with waste dregs from production of citric acid includes such technological steps as dewatering the waste dregs to obtain plaster, baking, grinding to obtain beta-type plaster, sieving by 1-8 cu.cm, high-pressure digestion, drying, grinding to obtain alpha-type gypsum, and low-temp drying (or natural drying) to obtain setting retarder, and features easily controlled technological process and conditions, high purity and quality of products, and reducing environmental pollution of the waste dregs.

Description

Utilize citric acid industrial waste residue to produce the method for gypsum series product
A kind of method of utilizing citric acid industrial waste residue to produce gypsum series product, belong to and produce the anhydrite technical field, be mainly used to utilize calcium salt method production industrial residue that citric acid produced to produce β type gypsum, α type terra alba and be used for the retardant of manufacture of cement.
In the prior art, mainly be by the exploitation natural resources as the gypsum of industrial raw material, it is big not only to exploit difficulty, the production cost height, and also production efficiency low-resource standing stock are also limited.But the industrial residue that is rich in the calcium sulfate composition on the other hand in the citric acid production in a large number abandoning in vain not only caused the waste and the loss of valuable industrial chemicals, but also polluted surrounding environment.
The object of the present invention is to provide a kind of technology simply can economical, rationally, effectively fundamentally solve in the citric acid production, turn waste into wealth again and utilize this waste residue to produce the method for gypsum series product because of the waste sludge discharge problem of environment pollution caused.
According to citric acid particularly the calcium salt method technical process of producing citric acid generally all be to utilize sulfuric acid and citrate of lime to react, generate citric acid and calcium sulfate, after extracting citric acid, be starchy calcium sulfate ejecta and be these characteristics of citric acid industrial waste residue, at the subject matter that exists in the prior art, basic design of the present invention is: producing the formed industrial residue of citric acid with above-mentioned calcium salt method is raw material, through the dehydration under the various boundary, oven dry or boiling, grind, β type gypsum is produced in the perhaps back air-dry processing that waits of dehydration respectively, α type terra alba and the gypsum series products such as retardant that are used for manufacture of cement.
The method of utilizing citric acid industrial waste residue to produce gypsum series product of the present invention, it is characterized in that this method comprises following process steps: (1) produces the formed industrial residue of citric acid with calcium salt method and injects dehydration generation plaster stone in the centrifuge, (2) plaster stone that above-mentioned (1) is generated is put into dryer heating, drying is to block under 150 °～300 ℃ conditions of temperature, and then to grind to form fineness be that 300 orders～350 purpose powderies are made β type powder gypsum; (3) selecting granularity from the block plaster stone that above-mentioned (1) dehydration generates is 1～8 centimetre 3The piece material and put it in the distilling kettle, feed steam at pressure 0.1～0.15MPa, boiling is 7～10 hours under 100 °～130 ℃ conditions of temperature, and then after under 120 °～220 ℃ conditions of temperature dry 2～3 hours, siccative being taken out that to grind to form fineness be that 300 orders～350 purpose powder are made α type terra alba, oven dry is the retardant that output is used for manufacture of cement to the plaster stone that (4) produce above-mentioned (1) under 80 ℃ of low temperature being lower than.
The above-mentioned step of making α type terra alba (3) also can directly feed heating water vapor that plaster stone produced pressurization voluntarily in the distilling kettle, promptly often say at ordinary times from platen press production.
The above-mentioned available natural air drying of output retardant step (4) and dry the replacement oven drying at low temperature.
The advantage that the present invention gives prominence to is: be raw material with the industrial residue, it is with low cost not only to turn waste into wealth, and has thoroughly solved citric acid waste residue problem of environment pollution caused, so the present invention has good economic benefit and social benefit.Again because the citric acid waste residue is fluid state, technological process and all control easily of processing condition as the raw material production gypsum series product, and higher purity is arranged, therefore the quality and the performance index of final product all are higher than GB, for example β type fineness can reach 310 orders, initial set 7 minutes, final set 11 minutes, anti-folding 5.2MPa, resistance to compression 12.8MPa; α type fineness can reach 315 orders, initial set 8 minutes, final set 13 minutes, anti-folding 21.1MPa, resistance to compression 54.2MPa.
One of most preferred embodiment of the present invention is: (1) is got calcium salt method and is produced the formed industrial residue of citric acid, dehydration generation water content is about 15% plaster stone in the injection centrifuge, (2) 10 kilograms of drying bakers of putting into 250 ℃ of plaster stone of getting above-mentioned (1) generation dried by the fire 3 hours, block drystone cream taking-up is ground to form 310 orders produce about 8.5 kilograms of β type terra albas; (3) get and be dewatered to 10 kilograms of block plaster stone, therefrom filter out 1～8 centimetre 3The piece material (remove seldom beyond the powder, basically complete is this block of material) and put it into the interior steam that feeds of distilling kettle at pressure 0.1MPa, boiling is 7 hours under 110 ℃ of conditions of temperature, and then siccative is taken out that to grind to form fineness be that 315 order powder production go out about 8.2 kilograms of α type terra albas after under 200 ℃ of conditions of temperature dry 2 hours; (4) get 10 kilograms of the plaster stone that above-mentioned (1) generates, about 9 kilograms of retardant were produced in oven dry in 1 hour under 80 ℃ of low temperature.
Change as present embodiment:
1, all temperature, pressure, times all can change in the scope of permission;
2, suitably modification is as pushing for used machinery of dehydration and method, and it is air-dry etc. that filter frame dewaters naturally;
3, α type terra alba can be used pressurization production voluntarily;
4, retardant can be used natural air drying, dries to replace oven dry.

Claims (3)

1, a kind of method of utilizing citric acid industrial waste residue to produce gypsum series product, it is characterized in that this method comprises following process steps: (1) produces the formed industrial residue of citric acid with calcium salt method and injects dehydration generation plaster stone in the centrifuge, (2) plaster stone that above-mentioned (1) is generated is put into dryer heating, drying is to block under 150 °～300 ℃ conditions of temperature, and then to grind to form fineness be that 300 orders～350 purpose powderies are made β type powder gypsum; (3) selecting granularity from the block plaster stone that above-mentioned (1) dehydration generates is 1～8 centimetre 3The piece material and put it in the distilling kettle, feed steam at pressure 0.1～0.15MPa, boiling is 7～10 hours under 100 °～130 ℃ conditions of temperature, and then after under 120 °～220 ℃ conditions of temperature dry 2～3 hours, siccative being taken out that to grind to form fineness be that 300 orders～350 purpose powder are made α type terra alba, oven dry is the retardant that output is used for manufacture of cement to the plaster stone that (4) produce above-mentioned (1) under 80 ℃ of low temperature being lower than.
2, the method for utilizing citric acid industrial waste residue to produce gypsum series product according to claim 1 is characterized in that the above-mentioned step of making α type terra alba (3) also can directly feed the heating water vapor that plaster stone produced pressurization voluntarily in the distilling kettle.
3, the method for utilizing citric acid industrial waste residue to produce gypsum series product according to claim 1 is characterized in that the above-mentioned available natural air drying of output retardant step (4) and dries the replacement oven drying at low temperature.
CN 97105654 1997-01-22 1997-01-22 Method for producing gypsum series product using citric acid industrial waste residue Pending CN1188747A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN 97105654 CN1188747A (en) 1997-01-22 1997-01-22 Method for producing gypsum series product using citric acid industrial waste residue

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN 97105654 CN1188747A (en) 1997-01-22 1997-01-22 Method for producing gypsum series product using citric acid industrial waste residue

Publications (1)

Publication Number Publication Date
CN1188747A true CN1188747A (en) 1998-07-29

Family

ID=5167970

Family Applications (1)

Application Number Title Priority Date Filing Date
CN 97105654 Pending CN1188747A (en) 1997-01-22 1997-01-22 Method for producing gypsum series product using citric acid industrial waste residue

Country Status (1)

Country Link
CN (1) CN1188747A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101230483B (en) * 2007-11-05 2010-06-09 安徽工业大学 Method for preparing gypsum whisker by calcium citrate
CN102584051A (en) * 2012-02-10 2012-07-18 潍坊英轩实业有限公司 Method for producing mixed gypsum powder by utilizing citric acid waste residue one-step process
CN102584052A (en) * 2012-02-10 2012-07-18 潍坊英轩实业有限公司 Method for producing alpha high-strength gypsum by utilizing citric acid waste residues

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101230483B (en) * 2007-11-05 2010-06-09 安徽工业大学 Method for preparing gypsum whisker by calcium citrate
CN102584051A (en) * 2012-02-10 2012-07-18 潍坊英轩实业有限公司 Method for producing mixed gypsum powder by utilizing citric acid waste residue one-step process
CN102584052A (en) * 2012-02-10 2012-07-18 潍坊英轩实业有限公司 Method for producing alpha high-strength gypsum by utilizing citric acid waste residues

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