CN1096007A - Produce the method and the device of hydrochloric acid from the methane heat chlorination reactant - Google Patents
Produce the method and the device of hydrochloric acid from the methane heat chlorination reactant Download PDFInfo
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- CN1096007A CN1096007A CN 93111836 CN93111836A CN1096007A CN 1096007 A CN1096007 A CN 1096007A CN 93111836 CN93111836 CN 93111836 CN 93111836 A CN93111836 A CN 93111836A CN 1096007 A CN1096007 A CN 1096007A
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- hydrochloric acid
- dilute hydrochloric
- membrance
- methane
- reactant
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Abstract
The invention discloses a kind of water and absorb the method that hydrogenchloride in the methane thermalization reactant is produced concentrated hydrochloric acid.It will be divided into (A, B) two portions from the reactant flow that chlorination reactor comes out, and the hydrogenchloride in two sections absorptions of first water (A) is produced dilute hydrochloric acid, and the hydrogenchloride that again dilute hydrochloric acid is cooled off in back two sections absorptions (B) is produced high density commodity hydrochloric acid.This invention has improved recovery of hydrogen chloride value in the methane heat chlorination reactant, is particularly suitable for producing with the methane heat chlorination method factory of methane chloride.
Description
The invention belongs to from the methane heat chlorination reactant water and reclaim hydrogenchloride and produce the particularly method of concentrated hydrochloric acid of hydrochloric acid, be applicable to that reclaiming the methane heat chlorination method produces the hydrogenchloride of by-product in the methane chloride process to produce high density commodity hydrochloric acid.
Produce methane chloride (CH in the methane heat chlorination method
3Cl, CH
2Cl
2, CHCl
3, CCl
4, be abbreviated as CMS jointly) technological process in, one mole of Cl of every consumption
2, just must generate one mole of HCl:
In the above-mentioned reaction process, when temperature of reaction was not high, reaction was undertaken by free radical lock reaction; When temperature of reaction was elevated to 370 ℃, the relativity of chain reaction mechanism lowered thereupon; Temperature of reaction surpasses 430 ℃, and the methane heat chlorination reaction is actually one and replaces irreversible bimolecular homogeneous reaction step by step.Four kinds of muriates generate simultaneously in the reaction process, so the chlorination of methane direct heat can not obtain single product.From the reactant flow that the thermal chlorination reactor comes out, different according to proportioning raw materials and reaction conditions can a certain methane chloride be main, but contain in other three kinds of methane chlorides, hydrogenchloride, methane, chlorine and raw materials impurity simultaneously (as C
2H
6Deng) product after the chlorination etc., make treating process become complicated.The representative component of main tetracol phenixin thermal chlorination reactant flow sees the following form:
Component title CCl
4CHCl
3CH
2Cl
2CH
3Cl HCl CH
4Cl
2N
2O
2
Content (%) 20.0 3.0 1.5 0.05 72.0 1.5 0.05 1.0 0.5
All the other still have a spot of CO
2, H
2O, 1.2-C
2H
2Cl
2, C
2HCl
3, C
2Cl
4, C
2Cl
6Deng.
Because hydrogenchloride has very strong corrodibility when containing steam, so the first step of refining reaction logistics is exactly the hydrogenchloride of removing wherein.Adopt two membrance-type absorber series connection carrying out secondaries to absorb on the general industry, flow process is as shown in Figure 1: the reactant flow M that comes out from the methane heat chlorination reactor is entered by first membrance-type absorber (1) top, contacts absorbing hydrogen chloride with absorption liquid that comes from second membrance-type absorber (2) bottom and stream; The gas that comes out from (1) bottom enters (2) top, contacts absorbing hydrogen chloride with absorption liquid that comes from afterbody tower (3) bottom and stream; The gas that comes out from (2) bottom enters (3) bottom, discharges behind service water with (3) top or the condensation of refrigerated water counter current contact, the remaining methane chloride of absorption and the hydrogenchloride.The service water or the refrigerated water that enter from afterbody tower (3) top, absorbing hydrogen chloride generates hydrochloric acid in afterbody tower (3), second membrance-type absorber (2) and first membrance-type absorber (1) successively, and concentration constantly raises.Membrance-type absorber (1), (2) all with water cooling to remove the heat that methane chloride condensation and hydrogenchloride are emitted when water-soluble.From the hydrochloric acid that comes out of (1) bottom, concentration is generally below 20%, and is entrained with the CMS of condensation, therefore will enter standing separation CMS in the crude salt acid separator (4).Hydrochloric acid behind the separation of C MS enters dilute hydrochloric acid storage tank (5).
Hydrochloric acid in the storage tank (5) (custom claims by-product hydrochloric acid) concentration is low, and the inconvenience transportation can not be satisfied concentrated hydrochloric acid user's requirement.A large amount of by-product hydrochloric acids of methane heat chlorination method factory have only personal or produce anhydrous HCl gas by stripping, are difficult to direct marketing.Even sell, its price is also far below industrial synthesis hydrochloric acid.
Purpose of the present invention: improve traditional technical process that hydrogenchloride is produced hydrochloric acid of from the methane heat chlorination reactant flow, reclaiming, improve the concentration of by-product hydrochloric acid, to reach the purpose of producing more than or equal to 35% commodity hydrochloric acid.
The present invention adopts two sections to absorb flow process, promptly increases the device of a cover as second section absorption, and with the corresponding separated into two parts of reactant flow that autoreactor comes out, imports two sections absorption units respectively.A part is undertaken by former technical process, after producing the by-product hydrochloric acid of lower concentration, enter hydrogen chloride gas in another part reactant of this flow process (this device) with absorption as the medium in second section flow process with this a part of hydrochloric acid again, thereby produce the commodity hydrochloric acid of high density, realize its goal of the invention.Concrete solution of the present invention is to set up a cover and the essentially identical second section absorption unit of original device behind the storage acid jar of former technical process, and this device comprises two membrance-type absorbers, a crude salt acid reactor, a concentrated hydrochloric acid basin, an afterbody tower; Except that adding between two membrance-type absorbers the water cooler, connecting mode each other is also identical with former absorption unit; First section absorption unit connects to import dilute hydrochloric acid with the afterbody tower of second absorption unit and the top of back one membrance-type absorber by water cooler, diluted acid pump and the pipeline of being located at behind the dilute hydrochloric acid basin; Also set up a crude salt acid separator between the afterbody tower bottom of these external two section apparatus and the recycle pump, a small amount of methane chloride and dilute hydrochloric acid with its discharge of Separation and Recovery, isolated dilute hydrochloric acid again by recycle pump after water cooler cooling, part input afterbody tower recycles, and one section dilute hydrochloric acid that another part and dilute hydrochloric acid pump come converges back input membrance-type absorber (8).
The method that the present invention adopts is: the reactant flow M that comes out from the thermal chlorination reactor is divided into (A, B) two portions, wherein a part (A) is by flow process shown in Figure 1, produce the lower concentration by-product hydrochloric acid, the hydrogenchloride that absorbs in another part reactant flow (B) with this by-product hydrochloric acid is produced concentrated hydrochloric acid again.Its whole process is as shown in Figure 2: reactant flow (A) is entered by first membrance-type absorber (1) top, contacts absorbing hydrogen chloride with absorption liquid and stream from second membrance-type absorber (2) bottom; The gas that comes out from (1) bottom enters (2) top, also flows by contacting absorbing hydrogen chloride with the absorption liquid that comes from afterbody tower (3) bottom; The gas that comes out from (2) bottom enters (3) bottom, discharges behind service water with (3) top or the condensation of refrigerated water counter current contact, the remaining methane chloride of absorption and the hydrogenchloride.The service water or the refrigerated water that enter from afterbody tower (3) top, absorbing hydrogen chloride generates hydrochloric acid in afterbody tower (3), second membrance-type absorber (2) and first membrance-type absorber (1) successively, and concentration constantly raises.From the hydrochloric acid that comes out of (1) bottom, acidity is generally at 13-15%, and is entrained with the CMS that condensation goes out, and behind crude salt acid separator (4) standing separation CMS, enters diluted acid storage tank (5).Content of the present invention is: the dilute hydrochloric acid in the diluted acid storage tank (5), after water cooler (6) cooling, deliver to the 4th membrance-type absorber (8) top through diluted acid pump (7), contact absorbing hydrogen chloride, improve concentration with gas that comes from tertiary membrane formula resorber (10) bottom and stream; Discharge from (8) bottom then, after water cooler (9) cooling, enter tertiary membrane formula resorber (10) top; Contact absorbing hydrogen chloride with reactant flow (B) of coming and stream, further improve concentration,, after entering crude salt acid separator (11) separating and condensing and going out CMS, enter concentrated hydrochloric acid storage tank (12) then from the discharge of (10) bottom from the thermal chlorination reactor.Reactant flow (B) is in membrance-type absorber (8), (10) after removing hydrogenchloride in, enter afterbody tower (13) bottom by membrance-type absorber (8) bottom, and discharge behind the dilute hydrochloric acid counter current contact condensation of cool off, the remaining methane chloride of absorption and the hydrogenchloride through supercooler (14).The dilute hydrochloric acid that is entrained with minute quantity CMS that discharge afterbody tower (13) bottom is after crude salt acid separator (15) leaves standstill, after using recycle pump (16) to deliver to water cooler (14) cooling again, a part enters the afterbody tower again and recycles, and enters membrance-type absorber (8) after the dilute hydrochloric acid that another part and diluted acid pump (7) are sent here converges.Crude salt acid separator (15) replenishes process water or river, and needn't use pure water.Industrial water cooling is all used in membrance-type absorber (1), (2), (8), (10).The water coolant that use water cooler (8), (9), (14), temperature is generally at 5-10 ℃.
The hydrochloric acid that adopts the present invention to produce, concentration (HCl meter) is more than or equal to 35%, and quality meets the listed every index of CNS GB 320-83 fully, and outward appearance is qualified, can satisfy some industrial sector needs, thereby can be used as commodity selling.The present invention compares with traditional technology, has not only improved the use value of by-product hydrochloric acid, and does not use high-quality pure water, can reduce cost, and makes the hydrochloric acid sale price improve more than 300%.
Accompanying drawing and description of drawings
Fig. 1 produces the hydrochloric acid schematic flow sheet for industrial from methane heat chlorination reactant recovery hydrogenchloride
Fig. 2 is a schematic flow sheet of the present invention
Among the figure:
(1). first membrance-type absorber (2). second membrance-type absorber
(3). afterbody tower (4). the crude salt acid separator
(5). dilute hydrochloric acid storage tank (6). water cooler
(7). diluted acid pump (8). the 4th membrance-type absorber
(9). water cooler (10). tertiary membrane formula resorber
(11). crude salt acid separator (12). the concentrated hydrochloric acid storage tank
(13). afterbody tower (14). water cooler
(15). crude salt acid separator (16). recycle pump
Embodiment:
With the 8000t/a tetracol phenixin is that the methane heat chlorination device of major product is an example:
Third and fourth membrance-type absorber (10), (8), crude salt acid separator (11), afterbody tower (13) all model, the specification with first section flow process (being former flow process) corresponding device are identical; It is 10m that area is adopted in water cooler (6), (9), (14)
2Graphite heat exchanger, diluted acid pump (7) and recycle pump (14) are the acid proof pump of FC65-50-160A type.Its technical process is, the reaction stream M that comes from the thermal chlorination reactor will be divided into A, B two portions, according to a certain percentage (A/B=0.8-1.2 is preferably 1) respectively from first, the top input of tertiary membrane formula resorber (1), (10).(the flow startup stage can be earlier to the input of A full flow, treat one section absorption unit output diluted acid after, when starting second section absorption unit, distribute reactant flow more according to the above ratio).Dilute hydrochloric acid from diluted acid storage tank (5), after water cooler (6) cooling, deliver to the 4th membrance-type absorber (8) top through diluted acid pump (7), the gas that comes bottom tertiary membrane formula resorber (10) also flows absorbing hydrogen chloride, concentration rises to 20-22%, reduce to through water cooler (9) cooling temperature and to enter reactant flow (B) and the stream that tertiary membrane formula resorber (10) and thermal chlorination reactor come after 25 ℃ and contact absorbing hydrogen chloride, concentration further is increased to more than 36%, discharge from (10) bottom then, after entering crude salt acid reactor (11) separating and condensing and going out CMS, enter concentrated hydrochloric acid storage tank (12) and store.The former by-product hydrochloric acid mean concns of this device 1987-1991 is 12.02%, and concentration of hydrochloric acid of the present invention is to check concentration still up to 36.40% after 37.12%, 47 day once more.The concentrated hydrochloric acid that the inventive method is produced is formed and national standard (industrial synthetic hydrochloric acid GB 320-83) contrast sees the following form.
H--35 index hydrochloric acid of the present invention among the Interventions Requested GB 320-83
Total acidity (HCl meter) % 〉=35.0 37.12
Iron %≤0.01＜0.01
Sulfate radical (SO4 meter) %≤0.007＜0.007
Arsenic %≤0.0001＜0.0001
Claims (5)
1, a kind of method and device of from the methane heat chlorination reactant, producing hydrochloric acid, its method comprises the methane heat chlorination reactant is divided into (A), (B) two portions, (A) successively through first membrance-type absorber (1), second membrance-type absorber (2) and afterbody tower (3), thereby the hydrogenchloride that water absorbs is wherein produced dilute hydrochloric acid, stores in dilute hydrochloric acid storage tank (5) behind crude salt acid separator (4) separation of C MS.Feature of the present invention is: the dilute hydrochloric acid in the dilute hydrochloric acid storage tank (5) is after water cooler (6) cooling, deliver to the 4th membrance-type absorber (8) top with dilute hydrochloric acid pump (7), contact absorbing hydrogen chloride with gas that comes from tertiary membrane formula resorber (10) bottom and stream, discharge from the 4th membrance-type absorber (8) bottom then, after water cooler (9) cooling, enter tertiary membrane formula resorber (10) top, contact absorbing hydrogen chloride with (B) and stream and generate concentrated hydrochloric acid, discharge from tertiary membrane formula resorber (10) bottom, enter concentrated hydrochloric acid storage tank (12) after entering crude salt acid separator (11) separation of C MS.
2, by described method and the device of from the methane heat chlorination reactant, producing hydrochloric acid of claim 1, it is characterized in that methane heat chlorination reactant (B) is at tertiary membrane formula resorber (10), after removing part hydrogenchloride in the 4th membrance-type absorber (8), enter afterbody tower (13) bottom, the dilute hydrochloric acid counter current contact of sending here with recycle pump (16) further removes hydrogenchloride, circulation dilute hydrochloric acid is discharged from afterbody tower (13), for recycle pump (16), send into and supply with afterbody tower (13) respectively after water cooler (14) cooling and the 4th membrance-type absorber (8) is made chlorine hydride absorbent after returning crude salt acid separator (15) separation of C MS and replenishing suitable quantity of water.
3, by claim 1 and 2 described method and the devices of from the methane thermal oxidation reactant, producing hydrochloric acid, it is characterized in that the water coolant that use water cooler (6), (9), (14), temperature is 5-10 ℃.
4, described by claim 1, from the methane heat chlorination reactant, produce the method and the device of hydrochloric acid, this device comprises one section absorption unit producing dilute hydrochloric acid with water as absorbing medium, it is characterized in that it comprises that also the dilute hydrochloric acid that comes with one section absorption unit is as second absorption unit of absorbing medium and the recirculation unit that connects with it; This absorption unit comprises two membrance-type absorbers, a crude salt acid separator, a concentrated hydrochloric acid basin and an afterbody tower; Connecting mode is except that adding between two membrance-type absorbers the water cooler each other, and all the other are all same with one section absorption unit; First section absorption unit then connects with the afterbody tower of second absorption unit and the top of back one membrance-type absorber by water cooler, diluted acid pump and the pipeline of being located at behind the dilute hydrochloric acid basin, to import dilute hydrochloric acid.
5, described by claim 4, from the methane heat chlorination reactant, produce the method and the device of hydrochloric acid, it is characterized in that, described recirculation unit is meant that afterbody tower (13) bottom successively forms the device that closed cycle is reclaimed with crude salt acid separator, recycle pump, water cooler and afterbody tower (13) top attachment by pipeline, separate a small amount of methane chloride and the dilute hydrochloric acid that this afterbody tower is discharged to reclaim, dilute hydrochloric acid recirculation is used.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93111836 CN1096007A (en) | 1993-05-31 | 1993-05-31 | Produce the method and the device of hydrochloric acid from the methane heat chlorination reactant |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93111836 CN1096007A (en) | 1993-05-31 | 1993-05-31 | Produce the method and the device of hydrochloric acid from the methane heat chlorination reactant |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1096007A true CN1096007A (en) | 1994-12-07 |
Family
ID=4989591
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 93111836 Pending CN1096007A (en) | 1993-05-31 | 1993-05-31 | Produce the method and the device of hydrochloric acid from the methane heat chlorination reactant |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1096007A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100460312C (en) * | 2006-09-20 | 2009-02-11 | 河北沧州大化集团有限责任公司 | Method of preparing hydrochloric acid using TDI byproduct hydrogen chloride gas and its device |
| CN103496670A (en) * | 2013-09-12 | 2014-01-08 | 聊城市鲁西化工工程设计有限责任公司 | HCl recovery technique |
| CN108218666A (en) * | 2017-12-25 | 2018-06-29 | 山东东岳氟硅材料有限公司 | A kind of method and retracting device that chloromethanes is recycled from by-product hydrochloric acid |
-
1993
- 1993-05-31 CN CN 93111836 patent/CN1096007A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100460312C (en) * | 2006-09-20 | 2009-02-11 | 河北沧州大化集团有限责任公司 | Method of preparing hydrochloric acid using TDI byproduct hydrogen chloride gas and its device |
| CN103496670A (en) * | 2013-09-12 | 2014-01-08 | 聊城市鲁西化工工程设计有限责任公司 | HCl recovery technique |
| CN103496670B (en) * | 2013-09-12 | 2015-05-13 | 聊城市鲁西化工工程设计有限责任公司 | HCl recovery technique |
| CN108218666A (en) * | 2017-12-25 | 2018-06-29 | 山东东岳氟硅材料有限公司 | A kind of method and retracting device that chloromethanes is recycled from by-product hydrochloric acid |
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|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
| WD01 | Invention patent application deemed withdrawn after publication |